CN108276554B - A kind of iron tailings modified aqueous polyurethane and preparation method thereof - Google Patents

A kind of iron tailings modified aqueous polyurethane and preparation method thereof Download PDF

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CN108276554B
CN108276554B CN201810092063.2A CN201810092063A CN108276554B CN 108276554 B CN108276554 B CN 108276554B CN 201810092063 A CN201810092063 A CN 201810092063A CN 108276554 B CN108276554 B CN 108276554B
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iron tailings
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aqueous polyurethane
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modified aqueous
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CN108276554A (en
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李凯斌
王书民
周春生
杨智婷
李盼
田鸽
李倩
任有良
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Shangluo University
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a kind of iron tailings modified aqueous polyurethanes and preparation method thereof, first pre-process iron tailings, add 80/ Tween 80 blended emulsifier of Span and are stirred to react, obtain modified iron tailings；Dimethylolpropionic acid is dissolved in acetone again, adds toluene di-isocyanate(TDI) and polycaprolactone glycol, reacts and base polyurethane prepolymer for use as is made；It is added modified iron tailings into base polyurethane prepolymer for use as, 70~80 DEG C of the reaction was continued 1~1.5h；It adds methacrylic acid -2- hydroxy methacrylate and carries out termination process；The pH value for finally adjusting reaction solution, adds water dispersion to obtain iron tailings modified aqueous polyurethane.The present invention selects 80/ Tween 80 blended emulsifier of Span to be surface-treated iron tailings, to improve the Miscibility of iron tailings inorganic matter Yu polyurethane high molecule material, prepare iron tailings modified aqueous polyurethane, the performances such as intensity, thermal stability, the water resistance of aqueous polyurethane product are effectively improved, and iron tailings can be consumed.

Description

A kind of iron tailings modified aqueous polyurethane and preparation method thereof
Technical field
The invention belongs to field of material preparation, in particular to a kind of iron tailings modified aqueous polyurethane and preparation method thereof.
Background technique
Aqueous polyurethane is to replace organic solvent as the new polyurethane system of decentralized medium using water, and also referred to as water dispersion is poly- Urethane, aqueous polyurethane or water-based polyurethane.Aqueous polyurethane takes water as a solvent, pollution-free, safe and reliable, mechanical performance is excellent Good, the advantages that compatibility is good, wearability is high, good toughness, strong, easily modified impact resilience.But its heat resistance and water resistance one As, so that application of the polyurethane on coating is subject to certain restrictions.In order to improve its service performance, the modification of polyurethane is ground Study carefully the extensive concern for having caused researcher, polyurethane material is carried out compound being that it is common using inorganic material such as silica One of method of modifying.[Liu Shijun, tension, the preparation of Shi Guang ultra-violet curing hybrid material and coupling agent influence research to Liu Shijun etc. The Guangdong [J] chemical industry, 2008, (03): 18-20] it is carried out in polyurethane by ethyl orthosilicate (TEOS) and silane coupling agent molten Glue-gel reaction obtains hybrid material, and heat resistance improves 5 DEG C, and as dioxide-containing silica increases, hot property is further It improves.
Tailing is the waste that Mineral Processing Enterprises choose that " useful constituent " discharges afterwards in mining process.According to incompletely statistics, Cut-off 2013, the mineral products of China's discovery have more than 150 kinds, and more than 8000 mines are established in exploitation, add up to generate 59.7 hundred million t of tailing. Comprehensive utilization of tailing rate is lower, its cumulant is caused still to be increasing year by year, and causes serious environmental pollution.The secondary resource of tailing Change to utilize and obtain the attention of various circles of society, and the research of tailing modified polyurethane is used to be rarely reported.
The main component of iron tailings is SiO2, also contain a small amount of Fe2O3、Al2O3, MgO, CaO etc. [Li Yanyi, be always on it is bright, The non-burning brick preparation of Li Chun iron tailings and performance study [J] Shangluo College journal, 2016, (06): 30-33], therefore, iron tail The physicochemical property of mine is similar to SiO2, be used for the modification of polyurethane, both can solve polyurethane material poor heat resistance and The problems such as poor water resistance, and can turn waste into wealth, realize green circulatory development.If but iron tailings and polyurethane high molecule is directly mixed Conjunction prepares composite material, and Miscibility is poor, will affect the stability of modified polyurethane.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, a kind of iron tailings modified aqueous polyurethane is provided And preparation method thereof, by being surface-treated to iron tailings, improve the body of iron tailings inorganic matter and polyurethane high molecule material It is compatibility, the good iron tailings modified aqueous polyurethane of preparation stability.
In order to achieve the above object, the present invention adopts the following technical scheme:
The following steps are included:
(1) iron tailings is pre-processed, adds 80/ Tween 80 blended emulsifier of Span and be stirred to react, is modified Iron tailings afterwards；Wherein the mass ratio of 80/ Tween 80 blended emulsifier of pretreated iron tailings and Span is 1:(10~15)；
(2) dimethylolpropionic acid is dissolved in acetone, adds toluene di-isocyanate(TDI) and polycaprolactone glycol, reaction is made Base polyurethane prepolymer for use as；It is added modified iron tailings into base polyurethane prepolymer for use as, 70~80 DEG C of the reaction was continued 1~1.5h；Again plus Enter methacrylic acid -2- hydroxy methacrylate and carries out termination process；The pH value for finally adjusting reaction solution, adds water dispersion to obtain iron tailings and changes Property aqueous polyurethane；Wherein the mass ratio between polycaprolactone glycol and modified iron tailings is 10:(0.2~0.4).
Further, in step (1), pretreatment is by iron tailings ball milling, and obtaining specific surface area is 800~1000m2/kg Powder, then in 100~110 DEG C of 3~4h of activation, it is spare to be finally cooled to room temperature.
Further, in step (1), 80/ Tween 80 blended emulsifier of Span be by Span 80 and Tween 80 in mass ratio (1~1.5): 1 is mixed to get.
Further, in step (1), 80/ Tween 80 blended emulsifier of Span is added and is stirred to react 80~100min.
Further, in step (2), dimethylolpropionic acid, toluene di-isocyanate(TDI), polycaprolactone glycol and metering system Mass ratio between acid -2- hydroxy methacrylate is (3~3.5): (8~9): 10:(3~4).
Further, in step (2), base polyurethane prepolymer for use as is obtained in 70~80 DEG C of 1~1.5h of reaction.
Further, it in step (2), is added in the reaction process of modified iron tailings, adds into base polyurethane prepolymer for use as It is glutinous to enter acetone drop；PH value is adjusted to 7~8 using triethanolamine.
Further, in step (2), when termination process, reaction temperature reacts 3~4h at 75~85 DEG C.
Further, in step (2), add water dispersion, adjust solid content to 35%~40%.
Iron tailings modified aqueous polyurethane made from preparation method as described above.
Compared with prior art, the invention has the following beneficial technical effects:
In preparation method of the present invention, iron tailings is modified using 80/ Tween 80 blended emulsifier of Span, (1) is adopted 80/ Tween 80 mixing and emulsifying agent molecule of Span has multiple ehter bonds (C-O-C) structure, the orphan that the oxygen atom on ehter bond has It is stronger to the active site compatibility of the ingredients such as oxide in electronics, with tailing, effectively iron tailings surface can be carried out It is modified；(2) 80/ Tween 80 mixing and emulsifying agent molecule of Span has multiple hydroxyls can be with polyurethane after being surface-treated to tailing The isocyanate group (- NCO) of molecule is reacted, and is divided greatly so that 80/ Tween 80 mixing and emulsifying agent molecule of Span is grafted to polyurethane In subchain, the compatibility of system is improved, therefore, 80/ Tween 80 blended emulsifier of Span to iron tailings be surface-treated after with Polyurethane synthetic system stability is preferable, and precipitation capacity is less；(3) specific toluene di-isocyanate(TDI) and polycaprolactone glycol are used Synthesis of polyurethane, and the iron tailings after surface treated is added in the synthesis process of polyurethane, that is to say, that at surface The monomer of iron tailings and polyurethane after reason coexists, the iron tail in polyurethane molecular chain during growth, after surface treatment Mine, which is equivalent to, provides a core, and realizes around the iron tailings of the continuous oriented attachment of urethane monomer after surface treatment The growth of strand, polyurethane molecular winding is even closer, intermolecular the effects of being formed by hydrogen bond power enhancing, when heated, It is difficult to decompose, so that the hot property of system is effectively improved.Molecular structure is even closer but also glue film obtained more causes It is close, make water be not easy to penetrate into, effectively improves water resistance.The method of the present invention selects 80/ Tween 80 blended emulsifier of Span to iron tail Mine is surface-treated, and to improve the Miscibility of iron tailings inorganic matter Yu polyurethane high molecule material, is prepared iron tailings and is changed Property aqueous polyurethane, is effectively improved the performances such as intensity, thermal stability, the water resistance of aqueous polyurethane product, and can consume iron tail Mine reduces the destruction to living environment, quality of improving the people's livelihood.Iron tailings modified aqueous polyurethane material produced by the present invention It has excellent performance, is mainly used for the fields such as water paint.
Further, the present invention adjusts solid content, and having can be improved product stability, reduces Product transport cost, with And it proposes high solid ratio and advantageously ensures that the advantages such as the performance of final products.
Specific embodiment
Preparation method of the present invention, comprising the following steps:
1) pretreatment of iron tailings:
First by iron tailings 30~40min of ball milling, obtaining specific surface area is 800~1000m2The powder of/kg, is put into baking oven 100~110 DEG C of 3~4h of activation, are cooled to room temperature, are put into drier, spare；Under stiring, into pretreated iron tailings 80/ Tween 80 blended emulsifier of Span is added dropwise, Span 80 and Tween 80 mass ratio are (1~1.5): 1, pretreated iron tail The mass ratio of mine and 80/ Tween 80 blended emulsifier of Span is 1:(10~15)；80~100min of reaction is stirred for get surface The iron tailings of modification.
2) preparation of iron tailings modified aqueous polyurethane:
The a certain amount of pure dimethylolpropionic acid of analysis is dissolved in acetone, wherein the mass ratio of dimethylolpropionic acid and acetone is 1: (1~1.5)；A certain amount of toluene di-isocyanate(TDI), polycaprolactone glycol are put into, 70~80 DEG C of 1~1.5h of reaction obtain poly- ammonia Ester performed polymer；The iron tailings of surface modification treatment is added into above-mentioned base polyurethane prepolymer for use as, 70~80 DEG C the reaction was continued 1~ 1.5h, it is glutinous to need to be added a small amount of acetone drop in reaction process, and gel is avoided to have an impact reaction process and product quality；Methyl is added 2-Hydroxy ethyl acrylate (HEMA) carries out termination process to base polyurethane prepolymer for use as, and reaction temperature controls the reaction at 75~85 DEG C 3~4h；PH to 7~8 is adjusted, adds water dispersion, adjusts solid content to 35%~40% to get the poly- ammonia of iron tailings modified water-soluble is arrived Ester.Wherein, dimethylolpropionic acid, toluene di-isocyanate(TDI), polycaprolactone glycol, modified iron tailings and methacrylic acid- Mass ratio between 2- hydroxy methacrylate is (3~3.5): (8~9): 10:(0.2~0.4): (3~4)；For drop glutinous acetone and The mass ratio of polycaprolactone glycol is (15~20): 10.
80/ Tween 80 mixing and emulsifying agent molecule of Span of the present invention has multiple ehter bonds (C-O-C) structure, In, 80 emulsifier molecules structural formula of Span are as follows:
Tween 80 emulsifier molecules structural formula are as follows:
Invention is further described in detail combined with specific embodiments below.
Embodiment 1:
1) pretreatment of iron tailings:
By iron tailings ball milling 30min, obtaining specific surface area is 800~1000m2The powder of/kg is put into 110 DEG C of work of baking oven Change 3h, is cooled to room temperature, is put into drier, it is spare；Under stiring, mass ratio is added dropwise into pretreated iron tailings is The 80/ Tween 80 blended emulsifier of Span of 1:1, is stirred for 100min to get the iron tailings of surface modification treatment, wherein pre-processing Iron tailings and 80/ Tween 80 blended emulsifier of Span mass ratio be 1:10.
2) preparation of iron tailings modified aqueous polyurethane:
3g dimethylolpropionic acid is dissolved in acetone, the mass ratio of dimethylolpropionic acid and acetone is 1:1；Put into 8g toluene two Isocyanates and 10g polycaprolactone glycol (molecular weight 1000), 80 DEG C of reaction 1h, obtain base polyurethane prepolymer for use as；To above-mentioned poly- ammonia It is added the iron tailings 0.3g of surface modification treatment in ester performed polymer, 80 DEG C of the reaction was continued 1h need that 15g acetone is added in reaction process Drop is glutinous；3g 2-hydroxyethyl methacry-late (HEMA) sealing end is added, reaction temperature is controlled at 80 DEG C, reacts 3h；Use triethanolamine PH to 8 is adjusted, adds water dispersion, adjusts solid content to 40% to get iron tailings modified aqueous polyurethane is arrived.
One of the main material that the present invention uses toluene di-isocyanate(TDI), containing rigid structures such as phenyl ring, with aliphatic chain Or the polyurethane of cyclic annular isocyanates synthesis is compared, the performances such as tensile strength, hardness are all preferable, and use methacrylic acid -2- Hydroxyl ethyl ester (HEMA) sealing end, products obtained therefrom moderate viscosity is preferable with iron tailings compatibility, achieves beneficial effect.
Embodiment 2:
1) pretreatment of iron tailings:
By iron tailings ball milling 30min, obtaining specific surface area is 800~1000m2The powder of/kg is put into 110 DEG C of work of baking oven Change 4h, is cooled to room temperature, is put into drier, it is spare；Under stiring, mass ratio is added dropwise into pretreated iron tailings is The 80/ Tween 80 blended emulsifier of Span of 1.2:1 is stirred for reaction 90min to get the iron tailings of surface modification treatment, wherein The mass ratio of iron tailings and 80/ Tween 80 blended emulsifier of Span is 1:15.
2) preparation of iron tailings modified aqueous polyurethane:
3.5g dimethylolpropionic acid is dissolved in acetone, the mass ratio of dimethylolpropionic acid and acetone is 1:1.2；Put into 9g first Phenylene diisocyanate and 10g polycaprolactone glycol (molecular weight 1000), 80 DEG C of reaction 1h, obtain base polyurethane prepolymer for use as；To above-mentioned It is added the iron tailings 0.35g of surface modification treatment in base polyurethane prepolymer for use as, 80 DEG C of the reaction was continued 1.5h need to be added in reaction process 20g acetone drop is glutinous；4g 2-hydroxyethyl methacry-late (HEMA) sealing end is added, reaction temperature is controlled at 75 DEG C, reacts 4h；With Triethanolamine adjusts pH to 7.5, adds water dispersion, adjusts solid content to 38% to get iron tailings modified aqueous polyurethane is arrived.
Embodiment 3:
1) pretreatment of iron tailings:
By iron tailings ball milling 35min, obtaining specific surface area is 800~1000m2The powder of/kg is put into 105 DEG C of work of baking oven Change 3.5h, is cooled to room temperature, is put into drier, it is spare；Under stiring, mass ratio is added dropwise into pretreated iron tailings For the 80/ Tween 80 blended emulsifier of Span of 1.4:1, it is stirred for reaction 80min to get the iron tailings of surface modification treatment, The mass ratio of middle iron tailings and 80/ Tween 80 blended emulsifier of Span is 1:14.
2) preparation of iron tailings modified aqueous polyurethane:
3.2g dimethylolpropionic acid is dissolved in acetone, the mass ratio of dimethylolpropionic acid and acetone is 1:1.4；Put into 8.6g Toluene di-isocyanate(TDI) and 10g polycaprolactone glycol (molecular weight 1000), 75 DEG C of reaction 1.2h, obtain base polyurethane prepolymer for use as；To It is added the iron tailings 0.2g of surface modification treatment in above-mentioned base polyurethane prepolymer for use as, 75 DEG C of the reaction was continued 1.2h are needed in reaction process It is glutinous that 18g acetone drop is added；3.2g 2-hydroxyethyl methacry-late (HEMA) sealing end is added, reaction temperature controls the reaction at 85 DEG C 3h；PH to 7.0 is adjusted with triethanolamine, adds water dispersion, adjusts solid content to 36% to get the poly- ammonia of iron tailings modified water-soluble is arrived Ester.
Embodiment 4:
1) pretreatment of iron tailings:
By iron tailings ball milling 40min, obtaining specific surface area is 800~1000m2The powder of/kg is put into 100 DEG C of work of baking oven Change 3.5h, is cooled to room temperature, is put into drier, it is spare；Under stiring, mass ratio is added dropwise into pretreated iron tailings For the 80/ Tween 80 blended emulsifier of Span of 1.5:1, it is stirred for reaction 85min to get the iron tailings of surface modification treatment, The mass ratio of middle iron tailings and 80/ Tween 80 blended emulsifier of Span is 1:12.
2) preparation of iron tailings modified aqueous polyurethane:
3.4g dimethylolpropionic acid is dissolved in acetone, the mass ratio of dimethylolpropionic acid and acetone is 1:1.5；Put into 8.4g Toluene di-isocyanate(TDI) and 10g polycaprolactone glycol (molecular weight 1000), 70 DEG C of reaction 1.5h, obtain base polyurethane prepolymer for use as；To It is added the iron tailings 0.4g of surface modification treatment in above-mentioned base polyurethane prepolymer for use as, 70 DEG C of the reaction was continued 1.5h are needed in reaction process It is glutinous that 16g acetone drop is added；3.6g 2-hydroxyethyl methacry-late (HEMA) sealing end is added, reaction temperature controls the reaction at 80 DEG C 3.5h；PH to 7.2 is adjusted with triethanolamine, adds water dispersion, adjusts solid content to 35% to get the poly- ammonia of iron tailings modified water-soluble is arrived Ester.
It will be using iron tailings modified aqueous polyurethane made from the method for the present invention and the iron tailings for not adding surface modification treatment The polyurethane of preparation is tested respectively, as a result such as the following table 1 to table 3:
The tensile strength data table of comparisons of 1 polyurethane film of table
The thermal weight loss rate data table of comparisons of 2 polyurethane film of table
The water absorption rate data table of comparisons of 3 polyurethane film of table
Sample Water absorption rate/%
The polyurethane of non-tailing mine preparation 220.5
The polyurethane for adding 0.2g tailing to prepare 118.4
Iron tailings modified aqueous polyurethane prepared by the present invention can preferably improve water it can be seen from upper table 1 to table 3 The performances such as intensity, thermal stability and the water resistance of property polyurethane product.
The present invention provides a kind of preparation methods of iron tailings modified aqueous polyurethane, use 80/ Tween 80 of Span first Blended emulsifier (mass ratio 1:1) is surface-treated iron tailings, spare；Pass through dimethylolpropionic acid, acetone, toluene two Isocyanates and polycaprolactone glycol react to obtain base polyurethane prepolymer for use as；Modified iron is added into above-mentioned base polyurethane prepolymer for use as The reaction was continued for tailing, and it is glutinous to need to be added a small amount of acetone drop in reaction process；Methacrylic acid -2- hydroxy methacrylate (HEMA) envelope is added End；PH is adjusted, water dispersion is added, adjusts solid content to get iron tailings modified aqueous polyurethane is arrived.Iron tailings prepared by the present invention changes Property aqueous polyurethane be mainly used for the fields such as water paint, and can turn waste into wealth, reduce destruction of the iron tailings to living environment, change Kind people's living standard.

Claims (9)

1. a kind of preparation method of iron tailings modified aqueous polyurethane, it is characterised in that: the following steps are included:
(1) iron tailings is pre-processed, adds 80/ Tween 80 blended emulsifier of Span and be stirred to react, obtains modified Iron tailings；Wherein the mass ratio of 80/ Tween 80 blended emulsifier of pretreated iron tailings and Span is 1:(10~15)；
(2) dimethylolpropionic acid is dissolved in acetone, adds toluene di-isocyanate(TDI) and polycaprolactone glycol, poly- ammonia is made in reaction Ester performed polymer；It is added modified iron tailings into base polyurethane prepolymer for use as, 70~80 DEG C of the reaction was continued 1~1.5h；Add first Base 2-Hydroxy ethyl acrylate carries out termination process；The pH value for finally adjusting reaction solution, adds water dispersion to obtain iron tailings modified water Property polyurethane；Wherein the mass ratio between polycaprolactone glycol and modified iron tailings is 10:(0.2~0.4)；
In step (1), pretreatment is by iron tailings ball milling, and obtaining specific surface area is 800~1000m2The powder of/kg, then 100 ~110 DEG C of 3~4h of activation, it is spare to be finally cooled to room temperature.
2. a kind of preparation method of iron tailings modified aqueous polyurethane according to claim 1, it is characterised in that: step (1) in, it is (1~1.5) that 80/ Tween 80 blended emulsifier of Span is by Span 80 and Tween 80 in mass ratio: 1 is mixed to get 's.
3. a kind of preparation method of iron tailings modified aqueous polyurethane according to claim 1, it is characterised in that: step (1) in, 80/ Tween 80 blended emulsifier of Span is added and is stirred to react 80~100min.
4. a kind of preparation method of iron tailings modified aqueous polyurethane according to claim 1, it is characterised in that: step (2) matter in, between dimethylolpropionic acid, toluene di-isocyanate(TDI), polycaprolactone glycol and methacrylic acid -2- hydroxy methacrylate Amount is than being (3~3.5): (8~9): 10:(3~4).
5. a kind of preparation method of iron tailings modified aqueous polyurethane according to claim 1, it is characterised in that: step (2) in, base polyurethane prepolymer for use as is obtained in 70~80 DEG C of 1~1.5h of reaction.
6. a kind of preparation method of iron tailings modified aqueous polyurethane according to claim 1, it is characterised in that: step (2) it in, is added into base polyurethane prepolymer for use as in the reaction process of modified iron tailings, it is glutinous that acetone drop is added；Using three ethyl alcohol Amine adjusts pH value to 7~8.
7. a kind of preparation method of iron tailings modified aqueous polyurethane according to claim 1, it is characterised in that: step (2) in, when termination process, reaction temperature reacts 3~4h at 75~85 DEG C.
8. a kind of preparation method of iron tailings modified aqueous polyurethane according to claim 1, it is characterised in that: step (2) in, add water dispersion, adjust solid content to 35%~40%.
9. iron tailings modified aqueous polyurethane made from preparation method as described in claim 1.
CN201810092063.2A 2018-01-30 2018-01-30 A kind of iron tailings modified aqueous polyurethane and preparation method thereof Active CN108276554B (en)

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CN106752851A (en) * 2017-03-09 2017-05-31 北京理工大学 A kind of preparation method of the composite modified aqueous polyurethane matting resin of organic/inorganic silicon

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CN105601885A (en) * 2015-12-30 2016-05-25 中物功能材料研究院有限公司 Ultraviolet curing water-based urethane acrylate and preparation method thereof
CN106752851A (en) * 2017-03-09 2017-05-31 北京理工大学 A kind of preparation method of the composite modified aqueous polyurethane matting resin of organic/inorganic silicon

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