WO2018141211A1 - 一种铸造水玻璃用固化剂 - Google Patents

一种铸造水玻璃用固化剂 Download PDF

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WO2018141211A1
WO2018141211A1 PCT/CN2018/073201 CN2018073201W WO2018141211A1 WO 2018141211 A1 WO2018141211 A1 WO 2018141211A1 CN 2018073201 W CN2018073201 W CN 2018073201W WO 2018141211 A1 WO2018141211 A1 WO 2018141211A1
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Prior art keywords
curing agent
water glass
weight
cast
ester
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PCT/CN2018/073201
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English (en)
French (fr)
Inventor
祝建勋
姚慧民
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济南圣泉集团股份有限公司
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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
Priority to MX2019009158A priority Critical patent/MX2019009158A/es
Priority to BR112019016079-5A priority patent/BR112019016079A2/pt
Priority to JP2019541789A priority patent/JP6963623B2/ja
Priority to EP18748129.6A priority patent/EP3613517B1/en
Priority to ES18748129T priority patent/ES2914315T3/es
Priority to US16/483,413 priority patent/US11253911B2/en
Priority to RU2019127453A priority patent/RU2741029C1/ru
Publication of WO2018141211A1 publication Critical patent/WO2018141211A1/zh
Priority to ZA201905669A priority patent/ZA201905669B/en

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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
    • B22C1/18—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 inorganic agents
    • B22C1/186—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 inorganic agents contaming ammonium or metal silicates, silica sols
    • B22C1/188—Alkali metal silicates
    • 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
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • 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
    • 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
    • B22C1/167—Mixtures of inorganic and organic binding agents
    • 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
    • B22C1/18—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 inorganic 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds

Definitions

  • the invention relates to the technical field of casting curing agent modification, in particular to a curing agent for casting water glass.
  • Casting is one of the most polluting industries in the machinery manufacturing industry, in which the binder for molding core is the main source of pollution.
  • the foundry employs widely used organic binders such as furan resin and urethane resin. When they are poured into the sand mold, they may release toxic gases and harmful substances such as toluene, xylene, phenol, carbon monoxide and suspended solids. In order to avoid emissions of decomposition products during the casting process, inorganic binders may be considered.
  • water glass is an inorganic binder synthesized from silica sand and soda ash. It is one of the most resource-rich substances on the earth and is the casting resin with the least impact on the environment. However, under the same amount of addition, the mechanical properties of the water glass binder are lower than that of the organic resin, and the water glass sand has poor collapsibility, which hinders its promotion and application. Therefore, the specific strength of the water glass is increased by adding a water glass reinforcing agent (a curing agent for casting water glass).
  • a water glass reinforcing agent a curing agent for casting water glass.
  • Amorphous silica can be used as the above water glass enhancer.
  • Chinese Patent Publication No. CN101027147A discloses a molding material mixture for preparing a sand mold for metal processing, which comprises a refractory molding base material and a water glass-based binder, wherein a certain proportion of the particulate amorphous type II Silicon oxide is added as a reinforcing agent to the binder.
  • the molding material mixture can greatly improve the strength of the sand mold after molding, the particulate amorphous silica as the reinforcing agent is a solid powder, and the continuity of the addition is poor, the metering and the addition are inconvenient; the dust is caused by the feeding.
  • the working environment deteriorates; especially when used in ester hardened water glass sand, the addition of multiple components increases the complexity of the operation and is therefore detrimental to industrial applications.
  • amorphous silica prepared by the decomposition of ZrSiO 4 heat amorphous silica (ZrSiO 4 pyrolysis amorphous silica) is preferable, since the same amount In the case of a higher core weight, this indicates that the sand particles are more densely packed. Further, in the preparation of the mixture, the amorphous silica prepared by the ZrSiO 4 thermal decomposition method exhibits particularly excellent properties, and the mixture has a lower viscosity and a better fluidity, and is more convenient to be added and used.
  • the above-mentioned ZrSiO4 thermal decomposition amorphous silica if it is stored in a liquid for more than three months, causes a sharp decrease in the bonding strength or even a self-hardening effect when it is used as a water glass curing agent.
  • an object of the present invention is to provide a curing agent for cast water glass which has strong adhesion strengthening effect, long shelf life and convenient operation, and a method for producing the curing agent for cast water glass and use.
  • the present invention includes:
  • a curing agent for cast water glass comprising: an ester and an amorphous silica of ZrSiO 4 thermal decomposition method; and the curing agent for cast water glass does not contain water.
  • the curing agent for cast water glass according to Item 1 which further comprises an alcohol.
  • the curing agent for cast water glass according to any one of the above aspects, wherein the weight ratio of the ester to the ZrSiO 4 thermal decomposition amorphous silica is from 0.78 to 3.2:1, preferably It is 1.0-2.5:1.
  • ester is selected from the group consisting of monoacetin, diacetin, triacetin, and ethylene glycol diacetate.
  • ester propylene carbonate, ⁇ -butyrolactone or a dibasic ester.
  • the curing agent for cast water glass according to any one of the items 2 to 5, wherein the alcohol is selected from the group consisting of ethanol, methanol, propanol, isopropanol, butanol, isobutanol, and benzyl alcohol.
  • the alcohol is selected from the group consisting of ethanol, methanol, propanol, isopropanol, butanol, isobutanol, and benzyl alcohol.
  • the curing agent for cast water glass according to any one of items 1 to 6, which is composed of an ester, an alcohol, and an amorphous silica of ZrSiO 4 thermal decomposition method.
  • the stirring speed is 800 rpm or more, and the ZrSiO 4 thermal decomposition amorphous silica weighed according to the ratio is added, and stirring is continued for 10-20 minutes to make a suspension, and the foundry water is obtained.
  • a curing agent for glass is 800 rpm or more, and the ZrSiO 4 thermal decomposition amorphous silica weighed according to the ratio is added, and stirring is continued for 10-20 minutes to make a suspension, and the foundry water is obtained.
  • a curing agent for glass is 800 rpm or more, and the ZrSiO 4 thermal decomposition amorphous silica weighed according to the ratio is added, and stirring is continued for 10-20 minutes to make a suspension, and the foundry water is obtained.
  • a water glass self-hardening sand wherein, relative to 100 parts by weight of the total amount of the self-hardening sand of the water glass, it comprises:
  • Curing agent for casting water glass 0.2-1.4 parts by weight
  • the curing agent for molten water glass is the hardening agent for cast water glass according to any one of item 1-7.
  • the present invention it is possible to provide a curing agent for cast water glass which has a strong adhesion reinforcing effect, a long shelf life, and is easy to handle, a method for producing a curing agent for cast water glass, and a use thereof.
  • the present invention provides a curing agent for casting a water glass (curing agent of the present invention) comprising:
  • the curing agent for cast water glass does not contain water.
  • ester means a product obtained by esterification of an alcohol with a carboxylic acid or an inorganic oxyacid, preferably a product obtained by esterification of an alcohol with an organic carboxylic acid.
  • the alcohol forming the ester ethylene glycol or glycerin (glycerol) is preferred.
  • carboxylic acid forming the ester acetic acid or an inorganic oxyacid (for example, carbonic acid) is preferred.
  • the ester contained in the curing agent of the present invention should be in a liquid state under normal conditions. Specific examples of the ester include, for example, monoacetin, diacetin, triacetin, ethylene glycol diacetate, propylene carbonate, ⁇ -butyrolactone or dibasic ester. One or more of them.
  • the curing agent of the present invention may further comprise an alcohol.
  • the unalcoholized curing agent is easy to be agglomerated during transportation, and requires a large speed to disperse, which makes it difficult to transfer and use the curing agent.
  • the inclusion of a certain amount of alcohol can not only make the curing agent of the present invention have a suitable viscosity, but also can be used after being transported or placed for a long time, and the original effect can be achieved after a slight stirring. Convenience.
  • the term "alcohol” means a compound in which an aliphatic hydrocarbon, an alicyclic hydrocarbon or a hydrogen atom on an aromatic hydrocarbon side chain is substituted with a hydroxyl group.
  • the alcohol contained in the curing agent of the present invention should be in a liquid state under normal conditions.
  • Specific examples of the alcohol include, for example, one or two selected from the group consisting of ethanol, methanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol, ethylene glycol, and polyethylene glycol. the above.
  • the alcohol is not very toxic and the polarity can be between water and ester.
  • a particularly preferred example is ethanol because the suspension of the curing agent of the present invention can be more uniformly stabilized when ethanol is used; and ethanol is also an optimum choice in terms of economy and environmental friendliness.
  • the ZrSiO 4 thermal decomposition amorphous silica is in the form of particles, and the particulate amorphous silica preferably has a particle size of less than 50 ⁇ m, more preferably less than 10 ⁇ m, particularly preferably less than 5 ⁇ m.
  • the particle size can be determined by sieving analysis, and the sieve residue on the sieve having a mesh size of 10 ⁇ m is particularly preferably less than 7% by weight, preferably less than 4% by weight.
  • the term "containing no water” means that at least water is not intentionally added to the curing agent of the present invention.
  • the components constituting the curing agent of the present invention may contain a trace amount of water which is usually allowed, but preferably before the curing agent of the present invention is produced. At least some or all of the water is removed.
  • the present inventors have found that the presence of water greatly impairs the adhesion-enhancing effect of the curing agent of the present invention, resulting in a significant decrease in the adhesion-enhancing effect after long-term storage.
  • the curing agent of the present invention preferably has a water content of less than 3% by weight, more preferably less than 2% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight, still more preferably less than 0.2% by weight, more It is preferably less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.02% by weight, still more preferably less than 0.01% by weight.
  • the term “contains” and “comprises” means that it may include other components in addition to the components.
  • the other component include additives commonly used by those skilled in the art, such as a coupling agent (for example, a silane coupling agent or a carbonate coupling agent).
  • a coupling agent for example, a silane coupling agent or a carbonate coupling agent.
  • "containing” or “comprising” may be replaced with a closed “for” or “consisting of”.
  • the curing agent of the present invention comprises: 35-65 parts by weight of an ester, 5-20 parts by weight of an alcohol, and ZrSiO 4 thermal decomposition amorphous silica 20 with respect to 100 parts by weight of the total amount of the curing agent of the present invention. - 45 parts by weight.
  • the weight ratio of the ester to the ZrSiO 4 thermal decomposition amorphous silica is preferably from 0.78 to 3.2:1, more preferably from 1.0 to 2.5:1. This allows the curing agent of the present invention to perform well in adhesion enhancement, shelf life, and operability.
  • the present invention provides a preparation method (manufacturing method of the present invention) for preparing a curing agent of the present invention, which comprises the steps of:
  • the stirring speed is 800 rpm or more, and the ZrSiO 4 thermal decomposition amorphous silica weighed according to the ratio is added, and stirring is continued for 10-20 minutes to make a suspension, and the foundry water is obtained.
  • a curing agent for glass is 800 rpm or more, and the ZrSiO 4 thermal decomposition amorphous silica weighed according to the ratio is added, and stirring is continued for 10-20 minutes to make a suspension, and the foundry water is obtained.
  • a curing agent for glass is 800 rpm or more, and the ZrSiO 4 thermal decomposition amorphous silica weighed according to the ratio is added, and stirring is continued for 10-20 minutes to make a suspension, and the foundry water is obtained.
  • by ratio means a weight ratio in the curing agent according to the above invention.
  • the number of rotations in the above step (3) is set to 800 rpm or more, and appropriate adjustment can be made, for example, in the range of 800 to 1000 rpm, preferably 900 to 1000 rpm.
  • the production method of the present invention may further comprise the step of introducing the other components, which may be separately supplied or together with the above ester or alcohol. It may be added or may be added to the above ester or alcohol. Preferably, the ester is added first and then the other components are added.
  • the present inventors have found that by preparing the curing agent of the invention by mixing the above components, it can be used for the one-time addition of the curing agent for the cast water glass when it is applied to the preparation of the water glass self-hardening sand, without powder pollution.
  • the utility model has the advantages of simple operation, convenient metering and adding, and is favorable for industrial production; moreover, even if the curing agent of the invention is used for more than 90 days, the adhesion enhancement effect is not weakened, and the strength of the water glass sand can be remarkably enhanced, and The sand mold or core produced can maintain high strength after storage for a long time after molding, and greatly improves the mechanical properties of the sand or core.
  • the invention provides the use of a curing agent of the invention for making a sand mold or core.
  • the sand mold or core is preferably used for metal casting, which is preferably cast steel.
  • the present invention provides a water glass self-hardening sand, wherein: relative to 100 parts by weight of the total amount of the self-hardening sand of the water glass, comprising: 95-98 parts by weight of quartz sand, water
  • the glass is 1.8 to 3.6 parts by weight
  • the curing agent for the cast water glass is 0.2 to 1.4 parts by weight
  • the curing agent for the cast water glass is the curing agent of the present invention.
  • the ZrSiO 4 thermal decomposition amorphous silica was purchased from Suizhong Hengxin Material Technology Co., Ltd., with a particle size of 0.5 ⁇ m (D50), the same below.
  • the ester is first added to the reaction tank, stirring is started, then the alcohol and other components are added, the stirring speed is adjusted at 900-1100 rpm, the amorphous silica is added, and stirring is continued for 20 minutes.
  • a curing agent for cast water glass according to each embodiment of the present invention is obtained.
  • the preparation method of the curing agent for cast water glass of each comparative example was the same as the hardening agent for cast water glass of the Example.
  • the curing agent for cast water glass prepared in the above examples and comparative examples was used for the preparation of water glass self-hardening sand.
  • the specific operation is as follows: the curing agent for each cast water glass is stored in an oven at 55 ° C for accelerated storage test, and after 18 days of storage (corresponding to storage at room temperature for 6 months), the strength is compared with the newly prepared sample. Weigh 1000g of Dalin Standard Sand, add the blade type laboratory sand mixer, add 5.31g of each of the above-mentioned casting water glass curing agents, stir for 1min, add water glass (modulus 2.3, solid content 40%) 20g, stir for 1 minute.
  • the samples baked in an oven at 55 ° C for 18 days showed only minor changes in strength compared to the newly prepared samples and did not affect the actual use.
  • the comparatively-cured water glass hardener was baked in an oven at 55 ° C for 18 days, and its adhesion-enhancing effect was remarkably lowered and could not be used. From this, it is understood that the curing agent for cast water glass of the present invention does not deteriorate its adhesion-enhancing effect after long-term storage.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Mold Materials And Core Materials (AREA)
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Abstract

一种铸造水玻璃用固化剂，其包含酯以及ZrSiO 4热分解法无定形二氧化硅，且该铸造水玻璃用固化剂中不包含水。能够提供一种粘结增强作用强、保质期长、操作方便的铸造水玻璃用固化剂。

Description

一种铸造水玻璃用固化剂 技术领域
本发明涉及铸造固化剂改性技术领域，尤其涉及一种铸造水玻璃用固化剂。
背景技术
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，铸造厂广泛采用呋喃树脂、脲烷树脂等有机粘结剂，它们在液态金属浇入砂型时燃烧分解可能释放出甲苯、二甲苯、苯酚、一氧化碳和悬浮物等有毒气体和有害物质。为了避免在浇铸过程期间分解产物的排放，可以考虑采用无机粘结剂。
典型地，水玻璃是由硅砂和纯碱合成的无机粘结剂，是地球上资源最丰富的物质之一，是对环境影响最小的铸造树脂。但是，在相同加入量下，水玻璃粘结剂的力学性能低于有机树脂，加上水玻璃砂溃散性差，阻碍了它的推广和应用。因此，通过加入水玻璃增强剂(铸造水玻璃用固化剂)，提高水玻璃的比强度。
无定型二氧化硅可以用作上述水玻璃增强剂。例如，中国专利公开号CN101027147A公开了一种用于制备金属加工用砂型的造型材料混合物，其包含耐火的造型基础材料和基于水玻璃的粘结剂，其中，将一定比例的颗粒状无定型二氧化硅作为增强剂加入到所述粘结剂中。该造型材料混合物虽然能够大幅提高成型后砂型的强度，但是，作为增强剂的颗粒状无定型二氧化硅是固体粉料，其加入的连续性差、计量和添加均不方便；加料时粉尘飞扬造成工作环境 恶化；尤其是在酯硬化水玻璃砂中使用时，多组分分别加入增加了操作的复杂性，因而不利于工业应用。
另一方面，与其它来源的无定形二氧化硅相比，通过ZrSiO 4热分解法制备的无定形二氧化硅(ZrSiO 4热分解法无定形二氧化硅)是优选的，因为在加入量相同的情况下能够获得更高的型芯重量，这表明砂型粒子的堆积更加紧密。此外在制备混合物时，ZrSiO 4热分解法制备的无定形二氧化硅显示出了特别优异的性能，其混合物粘度更低，流动性更好，加入使用更加方便。
但是，上述ZrSiO4热分解法无定形二氧化硅若在液体中保存超过三个月，则在将其用作水玻璃固化剂时，会导致粘结强度急剧降低甚至不能起到自硬作用。
因此，若将上述ZrSiO 4热分解法无定形二氧化硅制备成液体形式的水玻璃增强剂，则该水玻璃增强剂是否仍能发挥强的粘结增强作用，还存在悬念。
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粘结增强作用强、保质期长、操作方便的铸造水玻璃用固化剂，该铸造水玻璃用固化剂的制造方法及其用途。
本发明人为解决上述技术问题进行了深入研究，结果发现：通过使ZrSiO 4热分解法无定形二氧化硅存在于酯中而制备的铸造水玻璃用无水固化剂能够解决上述技术问题，从而完成了本发明。即，本发明包括：
1.一种铸造水玻璃用固化剂，其包含：酯以及ZrSiO 4热分解法无定形二氧化硅；且该铸造水玻璃用固化剂中不包含水。
2.根据项1所述的铸造水玻璃用固化剂，其还包含醇。
3.根据项1或2所述的铸造水玻璃用固化剂，其中，相对于所述铸造水玻璃用固化剂的总量100重量份，其包含：
酯 35-65重量份，
醇 5-20重量份，以及
ZrSiO 4热分解法无定形二氧化硅 20-45重量份。
4.根据项1～3中任一项所述的铸造水玻璃用固化剂，其中，所述酯和所述ZrSiO 4热分解法无定形二氧化硅的重量比为0.78-3.2∶1，优选为1.0-2.5∶1。
5.根据项1～4中任一项所述的铸造水玻璃用固化剂，其中，所述酯为选自单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、乙二醇二乙酸酯、碳酸丙烯酯、γ-丁内酯或二元酯中的一种或两种以上。
6.根据项2～5中任一项所述的铸造水玻璃用固化剂，其中，所述醇为选自乙醇、甲醇、丙醇、异丙醇、丁醇、异丁醇、苯甲醇、乙二醇或聚乙二醇中的一种或两种以上。
7.根据项1-6中任一项所述的铸造水玻璃用固化剂，其由酯、醇、以及ZrSiO 4热分解法无定形二氧化硅组成。
8.根据项1-7中任一项所述的铸造水玻璃用固化剂的制备方法，其包括以下步骤：
(1)先将按配比称量的酯加入高速搅拌机搅拌罐内，并进行搅拌；
(2)视需要，投入按配比称量好的醇；
(3)使搅拌速度在800转/分钟以上，加入按配比称量好的ZrSiO 4热分解法无定形二氧化硅，继续搅拌10-20分钟，使其成为悬浮液，得到所述的铸造水玻璃用固化剂。
9.根据项1-7中任一项所述的铸造水玻璃用固化剂的用途，其用于制造砂 型或型芯，所述砂型或型芯用于金属铸造，优选地，所述金属铸造是铸钢。
10.一种水玻璃自硬砂，其中，相对于所述水玻璃自硬砂的总量100重量份，其包含：
石英砂 95-98重量份，
水玻璃 1.8-3.6重量份，以及
铸造水玻璃用固化剂 0.2-1.4重量份；
其中，所述铸造水玻璃用固化剂为项1-7中任一项所述的铸造水玻璃用固化剂。
发明效果
根据本发明，能够提供一种粘结增强作用强、保质期长、操作方便的铸造水玻璃用固化剂，该铸造水玻璃用固化剂的制造方法及其用途。
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。
首先，在一个方面中，本发明提供一种铸造水玻璃用固化剂(本发明的固化剂)，其包含：
酯，以及
ZrSiO 4热分解法无定形二氧化硅；
且该铸造水玻璃用固化剂中不包含水。
在本说明书中，术语“酯”是指：醇与羧酸或无机含氧酸发生酯化反应生成的产物，优选是醇与有机羧酸发生酯化反应生成的产物。作为形成所述酯的醇，优选乙二醇或丙三醇(甘油)。作为形成所述酯的羧酸，优选乙酸或无机含氧酸(例如碳酸)。本发明的固化剂中所包含的酯在通常条件下应为液态。作为所述酯的具体例子，可以列举出例如选自单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、乙二醇二乙酸酯、碳酸丙烯酯、γ-丁内酯或二元酯中的一种或两种以上。
优选地，本发明的固化剂中还可以包含醇。未加醇的固化剂容易在运输途中板结成块，需要较大速度才能分散，对转移、使用该固化剂造成了困难。经过大量探索实验表明：包含一定量的醇不但可以使本发明的固化剂具有适宜的粘度，并且在运输或较长时间放置后产生的聚沉，经轻微搅拌后即可达到原有效果，使用方便。
在本说明书中，术语“醇”是指：是脂肪烃、脂环烃或芳香烃侧链上的氢原子被羟基取代而成的化合物。本发明的固化剂中所包含的醇在通常条件下应为液体状态。作为所述醇的具体例子，可以列举出例如选自乙醇、甲醇、丙醇、异丙醇、丁醇、异丁醇、苯甲醇、乙二醇或聚乙二醇中的一种或两种以上。所述醇的毒性不大，且极性能够介于水和酯之间。特别优选的例子是乙醇，因为使用乙醇时，能够使本发明的固化剂的悬浮液更加均一稳定；且从经济性、环保性方面来看，乙醇也是最优选择。
所述ZrSiO 4热分解法无定形二氧化硅为颗粒状，该颗粒状无定形二氧化硅的粒度优选为小于50μm，更优选为小于10μm，特别优选为小于5μm。粒度可以通过筛分分析而确定，在具有10μm的筛孔尺寸的筛上的筛分残留物特别优选为小于7重量％，优选为小于4重量％。
在本说明书中，术语“不包含水”是指：本发明的固化剂中至少未有意添加水。构成本发明的固化剂的各组分(例如所述酯、醇、ZrSiO 4热分解法无定形二氧化硅)中可以包含通常被允许的微量的水，但优选在制造本发明的固化剂前将其中的至少一部分或全部的水除去。本发明人发现，水的存在对本发明的固化剂的粘结增强作用有很大损害，导致其在长期保存后粘结增强作用显著降低。因此，本发明的固化剂的含水量优选低于3重量％、更优选低于2重量％、更优选低于1重量％、更优选低于0.5重量％、更优选低于0.2重量％、更优选低于0.1重量％、更优选低于0.05重量％、更优选低于0.02重量％、更优选低于0.01重量％。
在本说明书中，术语“含有”、“包含”，意指其除所述组分外，还可以包括其他组分。作为所述其他成分，可以列举出例如本领域技术人员通常使用的添加剂，例如偶联剂(例如硅烷偶联剂、碳酸酯偶联剂)等。此外，在本说明书中，作为一种实施方式，“含有”、“包含”的可以替换为封闭式的“为”或“由……组成”。
本发明人发现，当本发明的固化剂中的各组分之比在一定范围时，能够更好地实现本发明的技术效果。因此，优选相对于本发明的固化剂的总量100重量份，本发明的固化剂包含：酯35-65重量份，醇5-20重量份，以及ZrSiO 4热分解法无定形二氧化硅20-45重量份。此外，所述酯和所述ZrSiO 4热分解法无定形二氧化硅的重量比优选为0.78-3.2∶1，更优选为1.0-2.5∶1。这可以使本发明的固化剂在粘结增强作用、保质期、可操作方面均表现良好。
在另一个方面中，本发明提供一种制备本发明的固化剂的制备方法(本发明的制造方法)，其包括以下步骤：
(1)先将按配比称量的酯加入高速搅拌机搅拌罐内，并进行搅拌；
(2)视需要，投入按配比称量好的醇；
(3)使搅拌速度在800转/分钟以上，加入按配比称量好的ZrSiO 4热分解法无定形二氧化硅，继续搅拌10-20分钟，使其成为悬浮液，得到所述的铸造水玻璃用固化剂。
在本说明书中，“按配比”是指：按照上述本发明的固化剂中的重量比。
本发明的制备方法中，酯和醇的优选例子如上述。
上述步骤(3)中的转速设置为800转/分以上，例如可以在800-1000转/分、优选900-1000转/分的范围内进行适当的调整。
在本发明的固化剂还包含其它组分的情况下，本发明的制备方法还可以包含投入所述其它组分的步骤，所述其它组分可以单独投入，也可以与上述的酯或醇一起加入，或者可以混入上述的酯或醇中加入。优选先加入酯，然后再加入所述其它组分。
本发明人发现，通过将上述各组分混合制备成本发明的固化剂，可以在将其应用于水玻璃自硬砂的制备时，实现铸造水玻璃用固化剂的一次性加入，无粉体污染，操作简单，计量、添加方便，有利于工业化生产；而且，即使将本发明的固化剂保存超过90天再使用，其粘结增强作用不减弱，仍可显著增强水玻璃砂的强度，并使得所制造的砂型或型芯在成型后经较长时间的贮存仍能保持较高的强度，大大改善了砂型或型芯的力学性能。
虽然本发明的作用机制尚未明确，但一种解释是：在体系中存在水的情况下，ZrSiO 4热分解法无定形二氧化硅与水共同作用加速了酯的分解，而通过使体系中不包含水，酯的分解得到了抑制。
因此，在另一个方面中，本发明提供本发明的固化剂的用途，其用于制造砂型或型芯。所述砂型或型芯优选用于金属铸造，所述金属铸造优选是铸钢。
此外，在另一个方面中，本发明还提供一种水玻璃自硬砂，其中，相对于所述水玻璃自硬砂的总量100重量份，其包含：石英砂95-98重量份，水玻璃1.8-3.6重量份，以及铸造水玻璃用固化剂0.2-1.4重量份；所述铸造水玻璃用固化剂为本发明的固化剂。
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
Figure PCTCN2018073201-appb-000001
所述ZrSiO 4热分解法无定形二氧化硅购买自蚌埠中恒新材料科技有限公司，粒度0.5μm(D50)，下同。
实施例2
Figure PCTCN2018073201-appb-000002
Figure PCTCN2018073201-appb-000003
实施例3
Figure PCTCN2018073201-appb-000004
实施例4
Figure PCTCN2018073201-appb-000005
实施例5
Figure PCTCN2018073201-appb-000006
Figure PCTCN2018073201-appb-000007
实施例6
Figure PCTCN2018073201-appb-000008
实施例7
Figure PCTCN2018073201-appb-000009
Figure PCTCN2018073201-appb-000010
Figure PCTCN2018073201-appb-000011
各实施例中，先将所述酯加入反应罐，启动搅拌，然后加入所述醇和其它组分，调整搅拌转速在900-1100转/分钟，加入所述无定形二氧化硅，继续搅拌20min，得本发明各实施例的铸造水玻璃用固化剂。
对比例1
Figure PCTCN2018073201-appb-000012
对比例2
Figure PCTCN2018073201-appb-000013
Figure PCTCN2018073201-appb-000014
对比例3
Figure PCTCN2018073201-appb-000015
各对比例的铸造水玻璃用固化剂的制备方法同实施例的铸造水玻璃用固化剂。
对于上述实施例和对比例中制备的铸造水玻璃用固化剂，将其用于水玻璃自硬砂的制备。具体操作为：将各铸造水玻璃用固化剂存放于55℃烘箱中进行保存期加速试验，存放18天后(相当于室温存放6个月)与新配制的样品做强度对比。称取大林标准砂1000g，加入叶片式实验室用混砂机，分别加上述各铸造水玻璃用固化剂5.31g，搅拌1min，加水玻璃(模数2.3，固含量40％)20g，搅拌1分钟，出砂，打制成“8”形试块，检测1h，4h和24h抗拉强度，执行标准GB-2684，其结果如表1和表2所示。“8”形试块存放于20℃、40％(RH％)的恒温恒湿箱中。
表1
Figure PCTCN2018073201-appb-000016
Figure PCTCN2018073201-appb-000017
表2
Figure PCTCN2018073201-appb-000018
Figure PCTCN2018073201-appb-000019
如表1中的实施例所示，在55℃烘箱中烘18天的样品与新配制的样品相比，强度只有微小变化，不影响实际使用。但是，如表2中的对比例铸造水玻璃用固化剂在55℃烘箱中烘18天，其粘结增强作用已明显降低，无法使用。由此可知，本发明的铸造水玻璃用固化剂经长期保存后，其粘结增强作用不降低。

Claims (10)

  1. 一种铸造水玻璃用固化剂，其包含：酯以及ZrSiO 4热分解法无定形二氧化硅；且该铸造水玻璃用固化剂中不包含水。
  2. 根据权利要求1所述的铸造水玻璃用固化剂，其还包含醇。
  3. 根据权利要求1或2所述的铸造水玻璃用固化剂，其中，相对于所述铸造水玻璃用固化剂的总量100重量份，其包含：
    酯35-65重量份，
    醇5-20重量份，以及
    ZrSiO 4热分解法无定形二氧化硅20-45重量份。
  4. 根据权利要求1或2所述的铸造水玻璃用固化剂，其中，所述酯和所述ZrSiO 4热分解法无定形二氧化硅的重量比为0.78-3.2∶1，优选为1.0-2.5∶1。
  5. 根据权利要求1或2所述的铸造水玻璃用固化剂，其中，所述酯为选自单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、乙二醇二乙酸酯、碳酸丙烯酯、γ-丁内酯或二元酯中的一种或两种以上。
  6. 根据权利要求2所述的铸造水玻璃用固化剂，其中，所述醇为选自乙醇、甲醇、丙醇、异丙醇、丁醇、异丁醇、苯甲醇、乙二醇或聚乙二醇中的一种或两种以上。
  7. 根据权利要求1-6中任一项所述的铸造水玻璃用固化剂，其由酯、醇、以及ZrSiO 4热分解法无定形二氧化硅组成。
  8. 根据权利要求1-7中任一项所述的铸造水玻璃用固化剂的制备方法，其包括以下步骤：
    (1)先将按配比称量的酯加入高速搅拌机搅拌罐内，并进行搅拌；
    (2)视需要，投入按配比称量好的醇；
    (3)使搅拌速度在800转/分钟以上，加入按配比称量好的ZrSiO 4热分解法无定形二氧化硅，继续搅拌10-20分钟，使其成为悬浮液，得到所述的铸造水玻璃用固化剂。
  9. 根据权利要求1-7中任一项所述的铸造水玻璃用固化剂的用途，其用于制造砂型或型芯，所述砂型或型芯用于金属铸造，优选地，所述金属铸造是铸钢。
  10. 一种水玻璃自硬砂，其中，相对于所述水玻璃自硬砂的总量100重量份，其包含：
    石英砂95-98重量份，
    水玻璃1.8-3.6重量份，以及
    铸造水玻璃用固化剂0.2-1.4重量份；
    其中，所述铸造水玻璃用固化剂为权利要求1-7中任一项所述的铸造水玻璃用固化剂。
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US20200164426A1 (en) 2020-05-28
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