CN105801786A - Low-cost modified naphthalene-based superplasticizer with high slump-keeping property and preparation method thereof - Google Patents

Low-cost modified naphthalene-based superplasticizer with high slump-keeping property and preparation method thereof Download PDF

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CN105801786A
CN105801786A CN201610137935.3A CN201610137935A CN105801786A CN 105801786 A CN105801786 A CN 105801786A CN 201610137935 A CN201610137935 A CN 201610137935A CN 105801786 A CN105801786 A CN 105801786A
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parts
liquid
oil
superplasticizer
water
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CN105801786B (en
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董翠平
彭城
马丽涛
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Anhui Xin Solid Environmental Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16Sulfur-containing compounds
    • C04B24/20Sulfonated aromatic compounds
    • C04B24/22Condensation or polymerisation products thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

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

Abstract

The invention discloses a low-cost modified naphthalene-based superplasticizer with high slump-keeping property and a preparation method thereof. The superplasticizer is prepared from the following components in parts by weight: 120-130 parts of industrial naphthalene oil, 50-60 parts of 80% petroleum waste phenol residue, 100-120 parts of concentrated sulphuric acid, 40-80 parts of formaldehyde, 80-100 parts of 30% alkaline solution, 20-40 parts of 35% papermaking black liquor, 12-20 parts of sulphur dioxide and a right amount of water. The prepared superplasticizer is low in production cost, the preparation method is simple and short in period, the problem that cost of naphthalene-based chemical modification is always high is solved, mixed concrete is relatively soft, does not adhere to bottom and has better workability and slump-keeping property, and bleeding ratio is low, so that concrete reinforcement effect is obvious.

Description

Modified naphthalene superplasticizer that a kind of low cost height guarantor is collapsed and preparation method thereof
Technical field
The present invention relates to concrete material field, be specifically related to a kind of low cost height and protect the modification collapsed Naphthalene series high-efficiency water-reducing agent and preparation method thereof.
Background technology
Conventional concrete material is made up of cement, aggregate and water, along with civil engineering technology enters Step, high performance concrete has become the important component part of civil engineering material, has been widely used in During heavy construction, bridge and marine structure thing are built.Prepare high performance concrete it is crucial that efficiently Water reducer uses, and the use of high efficiency water reducing agent can increase concrete flowability and reduce concrete material Water consumption 20-30% in material, the application of high efficiency water reducing agent makes to prepare the concrete of high-durability energy Material is possibly realized, and high efficiency water reducing agent has become an important component part of high performance concrete. The high efficiency water reducing agent used the most both at home and abroad mainly has lignosulfonates high efficiency water reducing agent, naphthalene sulphur Several classes such as hydrochlorate high efficiency water reducing agent, acyclic superplasticizer, polycarboxylic acid series high efficiency water reducing agent. Naphthalene series high-efficiency water-reducing agent is relatively low because of its production cost, and can reduce concrete water amount 15-20%, Being the most most popular high efficiency water reducing agent, it is mainly composed of naphthalenesulfonateformaldehyde formaldehyde contracting Compound sodium salt, phase early 1960s succeeded in developing by Japanese Kao company, 70 years 20th century Start rapidly production and application for the later stage all over the world, cause the leap of cement concrete technology Development.
Naphthalene water reducer synthesis technique comparative maturity at present, but home products abroad produces with flower king etc. Moral character can also have gap, particularly in the compatibility of sodium sulphate content, chloride ion content and cement Etc. aspect there is also obvious gap.Although the research that naphthalene series high-efficiency water-reducing agent is at home is with application Have for many years, but the raising of such water reducer performance does not has important breakthrough to develop.How will have Deferred action, the chemical group of space steric effect introduce the molecular structure of naphthalene series high-efficiency water-reducing agent In, and optimal control naphthalene series high-efficiency water-reducing agent production technology will be such diminishing the most further The popular research of agent.General chemical modification cost is high, the cycle is long, so naphthalene system for a long time Water reducer is based on physical modification.
At present naphthalene system production and application be mostly that the raw materials such as crude naphthalene, concentrated sulphuric acid, formaldehyde, liquid caustic soda close Becoming, cost height, it is more difficult that crude naphthalene extracts, and production process power consumption is big, is seldom related to utilize respectively Plant waste liquid and carry out the academic research of naphthalene system synthesis.Sodium sulphate content in current domestic naphthalene water reducer Universal higher, easily separate out when temperature is low, use difficulty big.Domestic Coal Chemical Industry is more, yield Relatively big, but naphtalene oil produced by Coal Chemical Industry, wherein contain substantial amounts of naphthalene, complex disposal process, Consume energy big, big for environment pollution.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of low cost height and protect the modified naphthalene collapsed Series high-efficiency water-reducing agent and preparation method thereof.
For realizing object above, the present invention is achieved by the following technical programs:
A kind of low cost height protects the modified naphthalene superplasticizer collapsed, by following components by weight Formulated: industry naphtalene oil 120-130 part, oil waste phenol dregs 50-60 part of 80%, dense sulfur Acid 100-120 part, formaldehyde 40-80 part, 30% liquid caustic soda 80-100 part, 35% black liquid 20-40 part, sulfur dioxide 12-20 part, water are appropriate.
Preferably, the most formulated by following components: industry naphtalene oil 125 parts, 80% Oil waste phenol dregs 55 parts, concentrated sulphuric acid 109 parts, 60 parts of formaldehyde, 30% liquid caustic soda 90 parts, 35% black liquid 33 parts, sulfur dioxide 16 parts, water are appropriate.
Preferably, the most formulated by following components: industry naphtalene oil 122 parts, 80% Oil waste phenol dregs 54 parts, concentrated sulphuric acid 105 parts, 55 parts of formaldehyde, 30% liquid caustic soda 87 parts, 35% black liquid 27 parts, sulfur dioxide 15 parts, water are appropriate.
Low cost height protects the preparation method of the modified naphthalene superplasticizer collapsed, and comprises the following steps:
1) black liquid is heated to 60-75 DEG C, while stirring, is slowly introducing sulfur dioxide, The time of being passed through is 15-20min, is warming up to 90 DEG C after having led to, and is incubated 20min, obtains modified papermaking Black liquor;
2) oil waste phenol dregs is heated to 80-85 DEG C, drips a small amount of concentrated acid sulfonation 1-2h, fall Temperature, obtains sulfonated petroleum and gives up phenol liquid;
3) industry naphtalene oil is joined in reactor, be heated to 150-160 DEG C while stirring, drip Adding remaining concentrated sulphuric acid, time for adding is 30-40min, stirring, is incubated 3-4h, according to reactant System adds suitable quantity of water and is incubated hydrolysis 30-40min at 120 DEG C, is cooled to after having hydrolyzed 80-85 DEG C, adding step 2) sulfonated petroleum gives up phenol liquid, drips formaldehyde, drip at 85-115 DEG C Adding the time is 2-6h, adds step 1 after dropping at 95-110 DEG C) sulfonation black liquid, 2-6h it is incubated at 90-120 DEG C,
4) regulate pH to 7 with liquid caustic soda, lower the temperature and i.e. obtain product.
Preferably, described step 2) in concentrated sulphuric acid dripping quantity be the 1/3-1/4 of oil waste phenol dregs quality.
The method have the benefit that oil waste phenol dregs in 1. raw materials, black liquid, industry the making of naphtalene oil With, it is prevented effectively from the waste discharge pollution to environment, removes the cumbersome process of recycling from;2. After oil waste phenol dregs in raw material, papermaking wastewater are modified process, introduce hydroxyl, ether chain, Increasing sterically hindered after sulfonic groups etc., with oxymethylene polymerization, hydrophilic increases, and enhances concrete Guarantor collapse effect;3. can reduce the usage amount of sulphuric acid after black liquid sulfonation, reduce in water reducer The content of sodium sulfate so that the dispersive property of water reducer is good, the concrete flowability of mix is good, Concrete cracking is low;4., compared with conventional counterparts, high efficiency water reducing agent prepared by the present invention is raw Producing low cost, preparation method is simple, and the cycle is short, solves naphthalene system chemical modification cost all the time High problem.Do not grab at the end through the concrete of mix is relatively soft, have more preferable workability and collapsing property of guarantor, And bleeding rate is low, obvious to the reinforced effects of concrete.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below will knot Close the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely retouched State, it is clear that described embodiment is a part of embodiment of the present invention rather than whole realities Execute example.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creation The every other embodiment obtained under property work premise, broadly falls into the scope of protection of the invention.
Embodiment 1:
A kind of low cost height protects the modified naphthalene superplasticizer collapsed, by following components by weight Formulated: industry naphtalene oil 125 parts, the oil waste phenol dregs 55 parts of 80%, concentrated sulphuric acid 109 Part, 60 parts of formaldehyde, 30% liquid caustic soda 90 parts, 35% black liquid 33 parts, sulfur dioxide 16 Part, water appropriate.
Low cost height protects the preparation method of the modified naphthalene superplasticizer collapsed, and comprises the following steps:
1) black liquid is heated to 70 DEG C, is slowly introducing sulfur dioxide while stirring, is passed through Time is 18min, is warming up to 90 DEG C after having led to, and is incubated 20min, obtains modified black liquid;
2) oil waste phenol dregs is heated to 82 DEG C, drips the concentrated acid sulfonation 1.5h of 15 parts, fall Temperature, obtains sulfonated petroleum and gives up phenol liquid;
3) joining in reactor by industry naphtalene oil, be heated to 155 DEG C while stirring, dropping is surplus Remaining concentrated sulphuric acid, time for adding is 35min, stirring, is incubated 3.5h, adds according to reaction system Suitable quantity of water is incubated hydrolysis 35min at 120 DEG C, is cooled to 85 DEG C after having hydrolyzed, and adds step 2) Sulfonated petroleum gives up phenol liquid, drips formaldehyde at 110 DEG C, and time for adding is 5h, after dropping Step 1 is added at 105 DEG C) sulfonation black liquid, at 110 DEG C, it is incubated 4h;
4) regulate pH to 7 with liquid caustic soda, lower the temperature and i.e. obtain product.
The low cost height that embodiment 1 prepares is protected the modified naphthalene superplasticizer collapsed be applied to build Build engineering concrete, be that low cost height is protected the modified naphthalene superplasticizer collapsed with aqueous solution shape Formula is added in concrete mix, and its volume is the 0.8%-2.1% of cement weight, monitors diminishing The indices such as rate, bleeding rate, slump, sodium sulphate content.And select conventional on the market A naphthalene water reducer as a control group, detects water-reducing rate, bleeding under conditions of volume is consistent The indices such as rate, slump, sodium sulphate content.The results are shown in Table 1 and table 2.
Water-reducing rate, bleeding rate and sodium sulphate content correction data when table 1 water reducer volume is 1.2%
Slump correction data when table 2 water reducer volume is 1.2%
As can be seen from Table 1 and Table 2, in the case of water reducer volume is identical, embodiment 1 Various performance parameters be substantially better than matched group, wherein bleeding rate is only the 60% of matched group, and Slump loss is significant lower;Under conditions of solid content is identical, sulfur in embodiment 1 Acid sodium content is only 4-6%, then naphthalene system concentration is high, and the dispersive property of water reducer is good, and under low temperature Operation does not has crystal to separate out.The low cost height that embodiment 1 prepares is protected the modified naphthalene series collapsed and is efficiently subtracted Water preparation can improve the workability of concrete, effectively reduces concrete water bleeding segregation phenomenon, slump Degree loss is little, has good workability, protects collapsing property.
Embodiment 2:
A kind of low cost height protects the modified naphthalene superplasticizer collapsed, by following components by weight Formulated: industry naphtalene oil 122 parts, the oil waste phenol dregs 54 parts of 80%, concentrated sulphuric acid 105 Part, 55 parts of formaldehyde, 30% liquid caustic soda 87 parts, 35% black liquid 27 parts, sulfur dioxide 15 Part, water appropriate.
Low cost height protects the preparation method of the modified naphthalene superplasticizer collapsed, and comprises the following steps:
1) black liquid is heated to 70 DEG C, is slowly introducing sulfur dioxide while stirring, is passed through Time is 20min, is warming up to 90 DEG C after having led to, and is incubated 20min, obtains modified black liquid;
2) oil waste phenol dregs is heated to 82 DEG C, the dense sulfur of dropping oil waste phenol dregs quality 14 parts Acid sulfonation 2h, cooling, obtain sulfonated petroleum and give up phenol liquid;
3) joining in reactor by industry naphtalene oil, be heated to 152 DEG C while stirring, dropping is surplus Remaining concentrated sulphuric acid, time for adding is 32min, stirring, is incubated 3.5h, adds according to reaction system Suitable quantity of water is incubated hydrolysis 30min at 120 DEG C, is cooled to 80 DEG C after having hydrolyzed, and adds step 2) Sulfonated petroleum gives up phenol liquid, drips formaldehyde at 105 DEG C, and time for adding is 4.5h, after dropping Step 1 is added at 100 DEG C) sulfonation black liquid, at 100 DEG C, it is incubated 5h;
4) regulate pH to 7 with alkali liquor, lower the temperature and i.e. obtain product.
Embodiment 3:
A kind of low cost height protects the modified naphthalene superplasticizer collapsed, by following components by weight Formulated: industry naphtalene oil 120 parts, the oil waste phenol dregs 60 parts of 80%, concentrated sulphuric acid 100 Part, 80 parts of formaldehyde, 30% liquid caustic soda 80 parts, 35% black liquid 40 parts, sulfur dioxide 12 Part, water appropriate.
Low cost height protects the preparation method of the modified naphthalene superplasticizer collapsed, and comprises the following steps:
1) black liquid is heated to 75 DEG C, is slowly introducing sulfur dioxide while stirring, is passed through Time is 20min, is warming up to 90 DEG C after having led to, and is incubated 20min, obtains modified black liquid;
2) oil waste phenol dregs is heated to 85 DEG C, drips the concentrated acid sulfonation 2h of 20 parts, cooling, Sulfonated petroleum gives up phenol liquid;
3) joining in reactor by industry naphtalene oil, be heated to 160 DEG C while stirring, dropping is surplus Remaining concentrated sulphuric acid, time for adding is 40min, stirring, is incubated 3h, adds according to reaction system Suitable quantity of water is incubated hydrolysis 40min at 120 DEG C, is cooled to 85 DEG C after having hydrolyzed, and adds step 2) sulfonated petroleum gives up phenol liquid, drips formaldehyde at 110 DEG C, and time for adding is 2h, drips complete After at 110 DEG C add step 1) sulfonation black liquid, at 115 DEG C be incubated 6h;
4) regulate pH to 7 with alkali liquor, lower the temperature and i.e. obtain product.
Embodiment 4:
A kind of low cost height protects the modified naphthalene superplasticizer collapsed, by following components by weight Formulated: industry naphtalene oil 130 parts, the oil waste phenol dregs 50 parts of 80%, concentrated sulphuric acid 120 Part, 40 parts of formaldehyde, 30% liquid caustic soda 100 parts, 35% black liquid 20 parts, sulfur dioxide 20 Part, water appropriate.
Low cost height protects the preparation method of the modified naphthalene superplasticizer collapsed, and comprises the following steps:
1) black liquid is heated to 75 DEG C, is slowly introducing sulfur dioxide while stirring, is passed through Time is 15min, is warming up to 90 DEG C after having led to, and is incubated 20min, obtains modified black liquid;
2) oil waste phenol dregs is heated to 85 DEG C, drips the concentrated acid sulfonation 1h of 14 parts, cooling, Sulfonated petroleum gives up phenol liquid;
3) joining in reactor by industry naphtalene oil, be heated to 150 DEG C while stirring, dropping is surplus Remaining concentrated sulphuric acid, time for adding is 30min, stirring, is incubated 3h, adds suitable according to reaction system Amount water is incubated hydrolysis 35min at 120 DEG C, is cooled to 80 DEG C after having hydrolyzed, and adds step 2) Sulfonated petroleum gives up phenol liquid, drips formaldehyde at 95 DEG C, and time for adding is 2h, after dropping in Step 1 is added at 100 DEG C) sulfonation black liquid, at 105 DEG C, it is incubated 2h;
4) regulate pH to 7 with alkali liquor, lower the temperature and i.e. obtain product.
Embodiment 5:
A kind of low cost height protects the modified naphthalene superplasticizer collapsed, by following components by weight Formulated: industry naphtalene oil 128 parts, the oil waste phenol dregs 57 parts of 80%, concentrated sulphuric acid 113 Part, 65 parts of formaldehyde, 30% liquid caustic soda 95 parts, 35% black liquid 27 parts, sulfur dioxide 18 Part, water appropriate.
Low cost height protects the preparation method of the modified naphthalene superplasticizer collapsed, and comprises the following steps:
1) black liquid is heated to 60 DEG C, is slowly introducing sulfur dioxide while stirring, is passed through Time is 15min, is warming up to 90 DEG C after having led to, and is incubated 20min, obtains modified black liquid;
2) oil waste phenol dregs is heated to 82 DEG C, drips the concentrated acid sulfonation 1-2h of 17 parts, fall Temperature, obtains sulfonated petroleum and gives up phenol liquid;
3) joining in reactor by industry naphtalene oil, be heated to 150 DEG C while stirring, dropping is surplus Remaining concentrated sulphuric acid, time for adding is 35min, stirring, is incubated 4h, adds according to reaction system Suitable quantity of water is incubated hydrolysis 30min at 120 DEG C, is cooled to 82 DEG C after having hydrolyzed, and adds step 2) Sulfonated petroleum gives up phenol liquid, drips formaldehyde at 85 DEG C, and time for adding is 3h, after dropping in Step 1 is added at 95 DEG C) sulfonation black liquid, at 90 DEG C, it is incubated 4h;
4) regulate pH to 7 with alkali liquor, lower the temperature and i.e. obtain product.
It should be noted that in this article, the relational terms of such as first and second or the like is only Only it is used for separating an entity or operation with another entity or operating space, and not necessarily Require or imply and there is the relation of any this reality or suitable between these entities or operation Sequence.And, term " includes ", " comprising " or its any other variant are intended to nonexcludability Comprise, so that include the process of a series of key element, method, article or equipment not only Including those key elements, but also include other key elements being not expressly set out, or also include The key element intrinsic for this process, method, article or equipment.There is no more restriction In the case of, statement " including ... " key element limited, it is not excluded that including described wanting Process, method, article or the equipment of element there is also other identical element.
Above example only in order to technical scheme to be described, is not intended to limit;Although With reference to previous embodiment, the present invention is described in detail, those of ordinary skill in the art It is understood that the technical scheme described in foregoing embodiments still can be modified by it, Or wherein portion of techniques feature is carried out equivalent;And these amendments or replacement, not The essence making appropriate technical solution departs from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (5)

1. a low cost height protects the modified naphthalene superplasticizer collapsed, it is characterised in that by with Lower component is the most formulated: industry naphtalene oil 120-130 part, the oil of 80% give up phenol Slag 50-60 part, concentrated sulphuric acid 100-120 part, formaldehyde 40-80 part, 30% liquid caustic soda 80-100 part, 35% black liquid 20-40 part, sulfur dioxide 12-20 part, water are appropriate.
2. low cost height as claimed in claim 1 protects the modified naphthalene superplasticizer collapsed, its Be characterised by, the most formulated by following components: industry naphtalene oil 125 parts, 80% Oil waste phenol dregs 55 parts, concentrated sulphuric acid 109 parts, 60 parts of formaldehyde, 30% liquid caustic soda 90 parts, 35% black liquid 33 parts, sulfur dioxide 16 parts, water are appropriate.
3. low cost height as claimed in claim 1 protects the modified naphthalene superplasticizer collapsed, its Be characterised by, the most formulated by following components: industry naphtalene oil 122 parts, 80% Oil waste phenol dregs 54 parts, concentrated sulphuric acid 105 parts, 55 parts of formaldehyde, 30% liquid caustic soda 87 parts, 35% black liquid 27 parts, sulfur dioxide 15 parts, water are appropriate.
4. the low cost height as described in claim 1-3 is arbitrary protects the efficient diminishing of modified naphthalene series collapsed The preparation method of agent, it is characterised in that comprise the following steps:
1) black liquid is heated to 60-75 DEG C, while stirring, is slowly introducing sulfur dioxide, The time of being passed through is 15-20min, is warming up to 90 DEG C after having led to, and is incubated 20min, obtains modified papermaking Black liquor;
2) oil waste phenol dregs is heated to 80-85 DEG C, drips a small amount of concentrated acid sulfonation 1-2h, fall Temperature, obtains sulfonated petroleum and gives up phenol liquid;
3) industry naphtalene oil is joined in reactor, be heated to 150-160 DEG C while stirring, drip Adding remaining concentrated sulphuric acid, time for adding is 30-40min, stirring, is incubated 3-4h, according to reactant System adds suitable quantity of water and is incubated hydrolysis 30-40min at 120 DEG C, is cooled to after having hydrolyzed 80-85 DEG C, adding step 2) sulfonated petroleum gives up phenol liquid, drips formaldehyde, drip at 85-115 DEG C Adding the time is 2-6h, adds step 1 after dropping at 95-110 DEG C) sulfonation black liquid, 2-6h it is incubated at 90-120 DEG C;
4) regulate pH to 7 with liquid caustic soda, lower the temperature and i.e. obtain product.
5. low cost height as claimed in claim 4 protects the preparation side of the modified naphthalene superplasticizer collapsed Method, it is characterised in that described step 2) in concentrated sulphuric acid dripping quantity be oil waste phenol dregs quality 1/3-1/4。
CN201610137935.3A 2016-03-10 2016-03-10 A kind of low cost is high to protect the modified naphthalene superplasticizer and preparation method thereof to collapse Active CN105801786B (en)

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CN108484852A (en) * 2018-05-18 2018-09-04 萧县沃德化工科技有限公司 A kind of modified naphthalene series water-reducing agent of useless residue in the production process containing phenols
CN108503254A (en) * 2018-05-18 2018-09-07 萧县沃德化工科技有限公司 A kind of useless rosin in adhesive production process is used for modified naphthalene series water-reducing agent
CN108609887A (en) * 2018-05-18 2018-10-02 萧县沃德化工科技有限公司 The method that the spent lye of mercerization prepares modified naphthalene series water-reducing agent
CN111777731A (en) * 2020-06-15 2020-10-16 安徽鑫固环保股份有限公司 Modified high slump loss resistant naphthalene water reducer and preparation method thereof
CN112125564A (en) * 2020-06-15 2020-12-25 安徽鑫固环保股份有限公司 Naphthalene water reducer

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CN108484852A (en) * 2018-05-18 2018-09-04 萧县沃德化工科技有限公司 A kind of modified naphthalene series water-reducing agent of useless residue in the production process containing phenols
CN108503254A (en) * 2018-05-18 2018-09-07 萧县沃德化工科技有限公司 A kind of useless rosin in adhesive production process is used for modified naphthalene series water-reducing agent
CN108609887A (en) * 2018-05-18 2018-10-02 萧县沃德化工科技有限公司 The method that the spent lye of mercerization prepares modified naphthalene series water-reducing agent
CN111777731A (en) * 2020-06-15 2020-10-16 安徽鑫固环保股份有限公司 Modified high slump loss resistant naphthalene water reducer and preparation method thereof
CN112125564A (en) * 2020-06-15 2020-12-25 安徽鑫固环保股份有限公司 Naphthalene water reducer
CN112125564B (en) * 2020-06-15 2022-10-04 安徽鑫固环保股份有限公司 Naphthalene water reducer
CN111777731B (en) * 2020-06-15 2023-07-25 安徽鑫固环保股份有限公司 Modified naphthalene water reducer with high slump loss resistance and preparation method thereof

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