CN106478877B - A kind of copolymer and the preparation method and application thereof - Google Patents
A kind of copolymer and the preparation method and application thereof Download PDFInfo
- Publication number
- CN106478877B CN106478877B CN201510546239.3A CN201510546239A CN106478877B CN 106478877 B CN106478877 B CN 106478877B CN 201510546239 A CN201510546239 A CN 201510546239A CN 106478877 B CN106478877 B CN 106478877B
- Authority
- CN
- China
- Prior art keywords
- copolymer
- acrylate
- water
- acid
- constant pressure
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to chemical fields, disclose a kind of copolymer, which contains the structural unit of thiourea derivative offer shown in formula (I), by C3‑10Unsaturated carboxylic acid provide structural unit and by C4‑10Acrylate provide structural unit, wherein R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2‑10Aliphatic chain and it is therein it is at least one be undersaturated aliphatic chain.The invention also discloses the preparation methods of the copolymer, including：At 50 95 DEG C, monomer, initiator and molecular weight regulator are mixed, then the reaction was continued 1 4h at 75 95 DEG C.The invention also discloses copolymer made from the method and its applications in processing cycle water.The copolymer of the present invention has preferable inhibition, resistance calcium carbonate scale and steady zinc effect.
Description
Technical field
The present invention relates to a kind of copolymers and the preparation method and application thereof, and in particular, to a kind of copolymer, copolymer
The application of preparation method and the copolymer in circulating water treatment.
Background technology
Currently, it is still the common side for controlling metal erosion and fouling that corrosion inhibiting and descaling agent is added in recirculating cooling water system
Method.Phosphorus system water treatment agent because its is nontoxic, at a low price and with good inhibition and scale-inhibiting properties, absolute master is still accounted in water process at present
The status led.On the one hand, it is to solve corrosion and the scale problems of industrial circulating water system to have made huge positive contribution；Separately
On the one hand, because phosphorus system water treatment agent can bring a large amount of phosphorus-containing compound to industrial wastewater, the pollution of environment, thus people are caused
Begin one's study other " green products " to substitute it.In general, corrosion-mitigation scale-inhibition agent prescription is by inhibition component and scale inhibition point
Scattered group is divided into two parts composition.The excellent without phosphorus copolymer analog dirt dispersion agent kind of scale-inhibiting properties is more, wherein many in reality
It is applied successfully in the production of border.And the optional leeway of non-phosphate inhibitor of function admirable is smaller, and over more than 30 years, novel no-phosphate corrosion
Among agent is still in positive exploration, green corrosion inhibitor poly-aspartate and polycyclic oxygen that early 1990s are developed by the U.S.
Succinic acid, can be directly biodegradable, to water nonpollution, by the extensive attention of water treatment field, although they have one
Fixed corrosion inhibition, but be not the corrosion inhibiter of function admirable.In addition in organic amine corrosion inhibiter, imidazoline corrosion inhibitor, day
Right corrosion inhibiter modification and Compositional type non-phosphate inhibitor etc. have also carried out numerous studies, and it is slow that corrosion mitigating effect cannot reach phosphorus system
The corrosion mitigating effect of erosion agent is not applied on a large scale in the industrial production due to factors such as cost, dosage, technical problems.
CN 103627235A disclose a kind of acrylic acid antirusting paint, contain following raw materials：Acrylic resin, acetic acid
Cellulose, allylthiourea, epoxy resin, aluminium oxide, tributyl phosphate, cerium oxide, polytetrafluoroethylene (PTFE), triethanolamine, lemon
Sour hydrazine and iron oxide red.
CN1103343C is disclosed inhibits sulfide ore to recycle the new of valuable ore during froth flotation ore
The inhibitor of grain husk and the method that the inhibitor is used in froth flotation method.Novel inhibitor be (methyl) acrylamide,
The terpolymer of allylthiourea and (methyl) hydroxyalkyl acrylates.
However above two is not appropriate for being used as the anti-incrustation corrosion inhibitor of recirculated water using the polymer that thiourea derivative obtains.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of new copolymer and preparation method thereof and answer
With.
The present inventor is the study found that by thiourea derivative, unsaturated carboxylic acid and acrylate containing unsaturated bond
Copolymerization gained polymer be used for circulating water treatment, do not introduce in the case of containing phosphorus component to corrosion of carbon steel have preferable inhibition
Effect, while there is certain scale inhibition effect.
Therefore, to achieve the goals above, in a first aspect, the present invention provides a kind of copolymer, the copolymer contain by
Shown in formula (I) thiourea derivative provide structural unit, by C3-10Unsaturated carboxylic acid provide structural unit and by C4-10's
The structural unit that acrylate provides,
Wherein, R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2-10Aliphatic chain, the aliphatic chain is
Saturated or unsaturated and R1、R2、R3And R4At least one of be undersaturated aliphatic chain.
Second aspect, the present invention provides the preparation method of the copolymer described in first aspect, this method includes：In 50-
At 95 DEG C, monomer, initiator and molecular weight regulator are mixed, then the reaction was continued the 1-4h at 75-95 DEG C, wherein institute
It includes thiourea derivative, unsaturated carboxylic acid and acrylate to state monomer.
The third aspect, the present invention provides the copolymers made from the method described in second aspect.
Fourth aspect, the present invention provides the answering in processing cycle water of the copolymer described in first aspect or the third aspect
With.
Copolymer using the present invention can obtain preferable corrosion mitigating effect during circulating water treatment, while can also obtain
It obtains and preferably hinders calcium carbonate scale and steady zinc effect.The present invention can obtain preferable inhibition effect under conditions of not adding phosphorous medicament
Fruit, it is environmentally friendly and have larger economic benefit and social benefit.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, in the absence of explanation to the contrary, the term " limiting viscosity " used refers to individual molecule pair
The contribution of solution viscosity is the viscosity for reflecting polymer characteristics, and value does not become with concentration, and unit is deciliter/gram (dL/g), pole
Limit viscosity is often used as the measurement of molecular weight, is usually measured with capillary viscometer (such as Ubbelohde viscometer)；Unless stated otherwise
(such as embodiment), the content or weight involved in the present invention are in terms of effective content (content or weight of solute).
Copolymer provided by the invention contains the structural unit of thiourea derivative offer shown in formula (I), by C3-10(such as
C3、C4、C5、C6、C7、C8、C9、C10) unsaturated carboxylic acid provide structural unit and by C4-10(such as C4、C5、C6、C7、C8、C9、
C10) acrylate provide structural unit,
Wherein, R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2-10(such as C2、C3、C4、C5、C6、C7、C8、
C9、C10) aliphatic chain, the aliphatic chain is saturated or unsaturated and R1、R2、R3And R4At least one of to be undersaturated
Aliphatic chain.Preferably, copolymer of the invention is not phosphorous (element).
Wherein, the unsaturated carboxylic acid can be double bond containing carboxylic acid, it is preferable that the unsaturated carboxylic acid be acrylic acid,
At least one of maleic acid, methacrylic acid and methylene-succinic acid.The acrylate can be alkyl acrylate and/
Or acrylic acid hydroxy alkyl ester, it is preferable that the acrylate is methyl acrylate, ethyl acrylate, hydroxy-ethyl acrylate and third
At least one of olefin(e) acid hydroxypropyl acrylate.
Preferably, the unsaturated fatty chain be alkenyl or alkenylalkyl (such as allyl or acrylic), the saturation
Aliphatic chain is alkyl or hydroxyalkyl (such as ethoxy).It is highly preferred that the thiourea derivative is allylthiourea, acrylic sulphur
Urea, N, N'- diallyl -2- thiocarbamides, N, N'- diallyl -2- thiocarbamides, N- (2- ethoxys)-N'-2- Allyl thioureas and N-
At least one of (2- ethoxys)-N'-2- allylthioureas.
According to the present invention, the weight ratio of the thiourea derivative, unsaturated carboxylic acid and acrylate is preferably 1-6:0.5-
5:1.The weight ratio weight prepared between monomer used in copolymer " thiourea derivative, unsaturated carboxylic acid and acrylate "
Amount is than characterization.
According to the present invention, the limiting viscosity of the copolymer is preferably 0.05-0.2dL/g, more preferably 0.08-
0.16dL/g.The viscosity average molecular weigh of the copolymer is preferably 1000-20000, more preferably 5000-10000.
According to the preferred embodiment of the present invention, the copolymer is made of above structure unit.
The preparation method of copolymer provided by the invention includes：At 50-95 DEG C, by monomer, initiator and molecular weight tune
Section agent is mixed, then the reaction was continued the 1-4h at 75-95 DEG C, wherein the monomer includes thiourea derivative, unsaturated carboxylic acid
And acrylate.
In the present invention, the dosage and specific choice as the thiourea derivative of monomer, unsaturated carboxylic acid and acrylate are equal
As previously mentioned, details are not described herein.
According to the preferred embodiment of the present invention, the mode of the mixing is：
(a) solution of the solution of monomer and initiator is added dropwise in the solution of molecular weight regulator respectively, or
(b) solution of the solution of monomer and molecular weight regulator is added dropwise in the solution of initiator respectively, or
(c) solution of initiator is added dropwise in the mixed solution of molecular weight regulator and monomer.
Mixed mode (a), (b) or (c) in, rate of addition is not required particularly.For example, in mode (a), it is single
The rate of addition of the solution of body is 30-400mL/h, and the rate of addition of the solution of initiator is 5-120mL/h.It is single in mode (b)
The rate of addition of the solution of body is 30-400mL/h, and the rate of addition of the solution of molecular weight regulator is 5-120mL/h.Mode
(c) in, the rate of addition of the solution of initiator is 5-120mL/h.
It should be strongly noted that the mixed solution middle-molecular-weihydroxyethyl conditioning agent of mode (c) middle-molecular-weihydroxyethyl conditioning agent and monomer
Concentration can be 5-85g/L.The concentration of monomer can be in the mixed solution of mode (c) middle-molecular-weihydroxyethyl conditioning agent and monomer
0.25-0.7kg/L。
In a preferred embodiment of the invention, the mode of the mixing is：By the solution of the solution of monomer and initiator
It is added dropwise in the solution of molecular weight regulator respectively.In the preferred embodiment, the solution of solution and initiator to monomer
Rate of addition do not require particularly, it is contemplated that anticorrosion-antiscaling property more preferably copolymer is obtained, it is highly preferred that monomer is molten
The rate of addition of liquid is 30-400mL/h, further preferably 60-200mL/h.It is highly preferred that the dropwise addition speed of the solution of initiator
Degree is 5-120mL/h, further preferably 15-100mL/h.
In a preferred embodiment of the invention, at 50-95 DEG C, monomer, initiator and molecular weight regulator are carried out
Mixed mode is preferably the mode being added dropwise.It can be to be warming up to 75-95 DEG C (preferably 80-90 DEG C) when being added dropwise, it can also be straight
It is added dropwise at a temperature of being connected on 75-95 DEG C (preferably 80-90 DEG C).It is specifically described in mode (a) as an example below：It will be single
The mode that the solution of body and the solution of initiator are added dropwise to respectively in the solution of molecular weight regulator can be to heat up when being added dropwise
(it specifically, can start to be added dropwise at 50-70 DEG C, then heat up when being added dropwise, cause the temperature of reaction system after completion of dropwise addition
Up to 75-95 DEG C (preferably 80-90 DEG C)), or directly dripped at a temperature of 75-95 DEG C (preferably 80-90 DEG C)
Add.In the case of preferred, by the way of heating up when being added dropwise.
In a preferred embodiment of the invention, the monomer includes thiourea derivative, unsaturated carboxylic acid and acrylate,
The solution of the monomer can be the solution of the solution of thiourea derivative, the solution of unsaturated carboxylic acid and acrylate (when use
Individually it is added dropwise), or the mixed solution of thiourea derivative, unsaturated carboxylic acid and acrylate (is prepared three when use
At dropwise addition together after mixed solution).Under preferable case, monomer (thiourea derivative, unsaturated carboxylic acid and acrylate) is used
Mixed solution, it is highly preferred that a concentration of 0.3-1kg/L of the mixed solution of the monomer.It is well known by those skilled in the art that
The solution of unsaturated carboxylic acid can be by obtaining after mixing the acid anhydrides of unsaturated carboxylic acid with solvent, it is clear that the use of acid anhydrides also exists
In the scope of the present invention, this will not be detailed here.
In the present invention, the initiator can be used with conventional dosage, it is preferable that the dosage of the initiator is monomer
The 2-12% of total dosage.The concentration of the solution of the initiator can be 20-720g/L.
In the present invention, the type of the initiator is not required particularly, can be commonly used in the art various
Radical initiator, it is preferable that the initiator be (water solubility) persulfate, more preferably ammonium persulfate, potassium peroxydisulfate and
At least one of sodium peroxydisulfate, further preferably ammonium persulfate.
In the present invention, the molecular weight regulator can be used according to conventional dosage, it is preferable that the molecular-weight adjusting
The dosage of agent is the 2-12% of the total dosage of monomer.The concentration of the solution of the molecular weight regulator can be 20-720g/L.
In the present invention, to the type of the molecular weight regulator, there is no particular limitation, can be commonly used in the art each
Substance (reducing agent) of the kind with reproducibility, it is preferable that the molecular weight regulator is (water solubility) sulphite, (water solubility)
Pyrosulfite and (water solubility) C3-C6At least one of alkanol, more preferably sodium hydrogensulfite, potassium bisulfite, Jiao Ya
At least one of sodium sulphate, potassium metabisulfite and isopropanol (most preferably a kind of), further preferably sodium hydrogensulfite.Its
In, (water solubility) C3-C6Alkanol be preferably saturated alkoxides, such as C3、C4、C5Or C6Saturated alkoxides.
The present invention also provides the copolymers made from the above method.The limiting viscosity for the copolymer that the present invention obtains exists
In 0.05-0.2dL/g (preferably 0.08-0.16dL/g) range, there is excellent anticorrosion-antiscaling property, can make as corrosion inhibiter
With.
In addition, the present invention also provides the copolymers of aforementioned present invention (as non-phosphate inhibitor) in processing cycle water
Using.Wherein, the additive amount of the copolymer is preferably 10-100mg/L recirculated waters, more preferably 20-60mg/L recirculated waters.
The copolymer of the present invention can be with existing various antisludging agents (such as poly-aspartate, poly-epoxy succinic acid) and dispersion
Agent (such as sulfonic acid base co-polymer, carboxylic acid group polymer) is used cooperatively, since the copolymer of the present invention has preferable scale inhibitor
Performance can reduce the dosage of antisludging agent and dispersant when in use.When using the copolymer of the present invention, the antisludging agent
It can be lower 40-70% than conventional dosage with total dosage of dispersant.
The present invention will be described in detail by way of examples below.In the following Examples and Comparative Examples, allyl sulfide
Urea, Allyl thiourea, N, N'- diallyl -2- thiocarbamides and N- (2- ethoxys)-N'-2- Allyl thioureas are purchased from lark prestige
Science and Technology Ltd., effective content are 98 weight %；Ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sodium pyrosulfite, sulfurous
Sour hydrogen sodium, isopropanol are purchased from Beijing chemical reagents corporation, and analysis is pure；Acrylic acid recovers fine chemistry industry research institute purchased from Tianjin,
It analyzes pure；Maleic anhydride is purchased from Beijing Yili Fine Chemicals Co., Ltd., and analysis is pure；Methacrylic acid and methylene-succinic acid
Purchased from Shanghai Yi Kang chemical materials Co., Ltd；Methyl acrylate, ethyl acrylate, hydroxy-ethyl acrylate and hydroxypropyl acrylate
It is purchased from lark prestige Science and Technology Ltd., effective content is not less than 99 weight %.
In embodiment and comparative example, the assay method of solid content is as follows：
About 1.0g or so corrosion inhibiter samples are weighed, 0.0002g is accurate to, is placed in the flat weighing disk weighed, carefully shakes
It is dynamic that medicament is made to flow naturally, one layer of uniform film is formed in ware bottom, is then placed in electrically heated drying cabinet, is added since room temperature
Heat at 120 DEG C after dry 4h, weighs once every half an hour until constant weight.It takes out, is put into drier cooling after constant weight
To room temperature, weigh.
Solid content calculation formula is：Solid content=[(m2-m1)/m] × 100%
m2：Medicament after drying and weighing disk weight, g
m1：Weighing disk net weight, g
m：Weigh the quality of medicament, g
Embodiment 1
Pyrosulfurous acid is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 7.2g and 20ml water, starts stirring, sodium pyrosulfite is made fully to dissolve.Allyl sulfide is added in a constant pressure funnel
Urea 24.5g, methylene-succinic acid 18g, methyl acrylate 18g and 100ml water, shake up；Add in another constant pressure funnel
Enter ammonium persulfate 1.2g and 40ml water, shakes up；It starts to warm up, when temperature is increased to 50 DEG C, starts that two constant pressure additions are added dropwise
Liquid in funnel, while continuing to increase temperature to 80 DEG C, control rate of addition makes the liquid in two constant pressure funnels 1
It is added dropwise to complete in a hour, continues insulation reaction later 2 hours, stop experiment, it is cooling that product, the solid content of product are
29.4%.
Embodiment 2
Potassium peroxydisulfate is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
2.4g and 40ml water starts stirring, potassium peroxydisulfate is made fully to dissolve.Allyl thiourea is added in a constant pressure funnel
27.6g, maleic anhydride 21g, ethyl acrylate 12g and 100ml water, shake up；Sulfurous is added in another constant pressure funnel
Sour hydrogen sodium 6g and 20ml water, shakes up；It starts to warm up, when temperature is increased to 60 DEG C, starts to be added dropwise in two constant pressure funnels
Liquid, while continue increase temperature to 75 DEG C, control rate of addition keep the liquid in two constant pressure funnels small at 1.5
When it is interior be added dropwise to complete, continue insulation reaction 2 hours later, stop experiment, cooling product, the solid content of product is 30.1%.
Embodiment 3
It is lower that isopropanol is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
4.8g and 20ml water starts stirring.Be added in a constant pressure funnel allylthiourea 30.6g, methacrylic acid 24g,
Hydroxy-ethyl acrylate 6.1g and 100ml water, shakes up；Sodium peroxydisulfate 3.6g and 40ml are added in another constant pressure funnel
Water shakes up；It starts to warm up, when temperature is increased to 70 DEG C, starts the liquid being added dropwise in two constant pressure funnels, continue simultaneously
Temperature is increased to 95 DEG C, control rate of addition makes the liquid in two constant pressure funnels be added dropwise to complete within 0.5 hour, it
Subsequent continuous insulation reaction stops experiment after 1 hour, the solid content of cooling product, product is 30.5%.
Embodiment 4
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 3.6g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Allyl sulfide is added in a constant pressure funnel
Urea 33.7g, acrylic acid 18g, hydroxypropyl acrylate 9.2g and 100ml water, shake up；It was added in another constant pressure funnel
Ammonium sulfate 4.8g and 40ml water, shakes up；It starts to warm up, when temperature is increased to 50 DEG C, starts that two constant pressure funnels are added dropwise
In liquid, control rate of addition so that the liquid in two constant pressure funnels is added dropwise to complete within 1.5 hours, continue simultaneously
85 DEG C are warming up to, continues insulation reaction 3 hours later, stops experiment, cooling product, the solid content of product is 31.1%.
Embodiment 5
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 2.4g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Allyl sulfide is added in a constant pressure funnel
Urea 36.3g, methacrylic acid 18g, methyl acrylate 6g and 100ml water, shake up；It was added in another constant pressure funnel
Ammonium sulfate 6g and 40ml water, shakes up；It starts to warm up, when temperature is increased to 65 DEG C, starts to be added dropwise in two constant pressure funnels
Liquid, control rate of addition makes the liquid in two constant pressure funnels be added dropwise to complete within 1 hour, while continuing to increase
Temperature continues insulation reaction 3 hours later to 90 DEG C, stops experiment, and cooling product, the solid content of product is 29.8%.
Embodiment 6
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 1.2g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.N, N'- bis- are added in a constant pressure funnel
Allyl -2- thiocarbamides 24.5g, acrylic acid 30g, hydroxypropyl acrylate 6.1g and 100ml water, shake up；In another constant pressure addition
Sodium peroxydisulfate 7.2g and 40ml water is added in funnel, shakes up；It starts to warm up, when temperature is increased to 50 DEG C, starts to be added dropwise two
Liquid in constant pressure funnel, control rate of addition make the liquid in two constant pressure funnels be dripped within 2 hours
At, while continuing to increase temperature to 90 DEG C, and continue insulation reaction later 4 hours, stops experiment, it is cooling that product, product are consolidated
Content is 30.6%.
Embodiment 7
Pyrosulfurous acid is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 4.8g and 20ml water, starts stirring, sodium pyrosulfite is made fully to dissolve.N- (2- hydroxyls are added in a constant pressure funnel
Ethyl)-N'-2- Allyl thioureas 27.6g, maleic anhydride 24g, ethyl acrylate 9g and 100ml water, shake up；In another perseverance
It presses and ammonium persulfate 2.4g and 40ml water is added in dropping funel, shake up；It starts to warm up, when temperature is increased to 55 DEG C, starts to drip
The liquid in two constant pressure funnels, control rate of addition is added to make the liquid in two constant pressure funnels within 2 hours
It is added dropwise to complete, while continuing to increase temperature to 85 DEG C, continue insulation reaction 2 hours later, stop experiment, cooling product, production
The solid content of product is 30.7%.
Embodiment 8
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 5.6g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Acrylic sulphur is added in a constant pressure funnel
Urea 24.5g, methylene-succinic acid 27g, hydroxy-ethyl acrylate 9g and 100ml water, shake up；Add in another constant pressure funnel
Enter potassium peroxydisulfate 3.6g and 40ml water, shakes up；It starts to warm up, when temperature is increased to 70 DEG C, starts simultaneously at and two constant pressures are added dropwise
Liquid in dropping funel, control rate of addition make the liquid in two constant pressure funnels be added dropwise to complete within 1.5 hours,
Continue to increase temperature simultaneously to 90 DEG C, continue insulation reaction 2 hours later, stops experiment, cooling product, the solid content of product
It is 29.8%.
Embodiment 9
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 1.2g, allylthiourea 30.6g, maleic anhydride 18g, hydroxypropyl acrylate 12g and 120ml water, start stirring, make each substance
Fully dissolving.Ammonium persulfate 1.2g and 25ml water is added in a constant pressure funnel, shakes up；It starts to warm up, when temperature liter
When height is to 60 DEG C, the liquid being added dropwise in constant pressure funnel is started simultaneously at, control rate of addition makes the liquid in constant pressure funnel
Body is added dropwise to complete within 1.5 hours, while continuing to increase temperature to 80 DEG C, is continued insulation reaction later 2 hours, is stopped examination
It tests, cooling product, the solid content of product is 29.7%.
Embodiment 10
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 7.2g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Allyl sulfide is added in a constant pressure funnel
Urea 36.7g, acrylic acid 12g, methyl acrylate 12g and 110ml water, shake up；Over cure is added in another constant pressure funnel
Sour ammonium 7.2g and 40ml water, shake up；It starts to warm up, when temperature is increased to 50 DEG C, starts simultaneously at two constant pressure addition leakages of dropwise addition
Liquid in bucket, control rate of addition make the liquid in two constant pressure funnels be added dropwise to complete within 1.5 hours, while after
High-temperature of continuing rising continues insulation reaction 3 hours later to 95 DEG C, stops experiment, cooling that product, the solid content of product are
30.4%.
Embodiment 11
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 6g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Allyl thiourea is added in a constant pressure funnel
30.6g, maleic anhydride 12g, hydroxypropyl acrylate 18.4g and 100ml water, shake up；It is added in another constant pressure funnel
Ammonium persulfate 3.6g and 40ml water, shakes up；It starts to warm up, when temperature is increased to 60 DEG C, starts that two constant pressure addition leakages are added dropwise
Liquid in bucket, control rate of addition make the liquid in two constant pressure funnels be added dropwise to complete within 1.5 hours, while after
High-temperature of continuing rising continues insulation reaction 2 hours later to 80 DEG C, stops experiment, cooling that product, the solid content of product are
29.7%.
Embodiment 12
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 2.4g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Allyl sulfide is added in a constant pressure funnel
Urea 27.6g, acrylic acid 15g, hydroxypropyl acrylate 18.4g and 100ml water, shake up；It is added in another constant pressure funnel
Ammonium persulfate 7.2g and 40ml water, shakes up；It starts to warm up, when temperature is increased to 50 DEG C, starts simultaneously at two constant pressure drops of dropwise addition
Liquid in liquid funnel, control rate of addition make the liquid in two constant pressure funnels be added dropwise to complete within 1.5 hours, together
Shi Jixu increases temperature to 95 DEG C, continues insulation reaction later 3 hours, stops experiment, cooling that product, the solid content of product are
30.4%.
Comparative example 1
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 3.6g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Acrylic acid is added in a constant pressure funnel
40g, hydroxypropyl acrylate 20.4g and 100ml water, shake up；In another constant pressure funnel be added ammonium persulfate 4.8g and
40ml water, shakes up；It starts to warm up, when temperature is increased to 50 DEG C, starts the liquid being added dropwise in two constant pressure funnels, control
Rate of addition makes the liquid in two constant pressure funnels be added dropwise to complete within 1.5 hours, while being continuously heating to 85 DEG C, it
Subsequent continuous insulation reaction 3 hours stops experiment, and the solid content of cooling product, product is 30.6%.
Comparative example 2
Copolymer is prepared according to the method for embodiment 4, unlike, " acrylic acid " is replaced with " acrylamide ", is obtained
The solid content of product is 30.1%.
Comparative example 3
Bisulfite is added into the four-hole boiling flask equipped with blender, reflux condenser, constant pressure funnel and thermometer
Sodium 3.6g and 20ml water, starts stirring, sodium hydrogensulfite is made fully to dissolve.Allyl sulfide is added in a constant pressure funnel
Urea 47.9g, hydroxypropyl acrylate 13.32g and 100ml water, shake up；Ammonium persulfate is added in another constant pressure funnel
4.8g and 40ml water, shakes up；It starts to warm up, when temperature is increased to 50 DEG C, starts the liquid being added dropwise in two constant pressure funnels
Body, control rate of addition make the liquid in two constant pressure funnels be added dropwise to complete within 1.5 hours, are continuously heating to simultaneously
85 DEG C, continue insulation reaction 3 hours later, stop experiment, cooling product, the solid content of product is 30.6%.
Test case 1
This test case is used for illustrating the performance of the copolymer obtained by above-described embodiment and comparative example.
Limiting viscosity and the scale inhibition for measuring the copolymer that each embodiment and comparative example obtains in accordance with the following methods respectively are slow
Corrosion energy, experiment Chinese medicine dosage is 10mg/L, and the results are shown in Table 2, and in table 2, "/" expression is not measured.
(1) measurement of limiting viscosity
Take corrosion inhibiter sample in culture dish, with the pH value of 80g/L sodium hydroxide solution adjusting sample solution to 9.0, so
After be put into baking oven and toast 4h at 120 ± 2 DEG C, taking-up, which is placed in drier, to be cooled to room temperature, that is, dry sample is made.It weighs
0.27g dries sample, is accurate to 0.0002g, with beaker, after being dissolved with 101g/L sodium thiocyanate solutions, is transferred to 50mL appearances
In measuring bottle, scale is settled to sodium thiocyanate solution, is shaken up, test solution.This liquid is added through the acidproof filtration funnels of G3
In the Ubbelohde viscometer of clean dried, until filling between graticule G, H, 10~15min of constant temperature is sucked test solution with rubber pipette bulb
C ball graticules E or more, even if reading the time of test solution outflow graticule E, F with stopwatch, three times, error is no more than 0.2s to METHOD FOR CONTINUOUS DETERMINATION,
Take its average value ts.It is carried out at the same time the blank assay t of sodium thiocyanate solution0s。
Limiting viscosity calculation formula is：Limiting viscosity={ 2 [(t/t0-1)-㏑t/t0]}1/2/C
t0：Sodium thiocyanate solution flows through the time of viscosimeter graticule E, F, s
t：Test solution flows through the time of viscosimeter graticule E, F, s
C：The concentration of test solution, g/dL
(2) measurement of calcium carbonate scale performance is hindered
Distilled water is taken to prepare Ca2+The test water of a concentration of 600mg/L, basicity 600mg/L, pH value 9.0 or so, will
Prepared corrosion inhibiter sample is added thereto, the residue Ca in standing 10h in 80 ± 1 DEG C of waters bath with thermostatic control, sampling analysis water2+It is dense
Degree, while blank sample is done, and calculate scale inhibition performance.
Scale inhibition performance calculation formula is：Scale inhibition performance=(C-C0) × 100%/(C1-C0)
C：Survey Ca2+Concentration (mg/L)
C0：The Ca of blank sample2+Concentration (mg/L)
C1：Ca in raw water2+Concentration (mg/L)
(3) stablize the measurement of zinc salt performance
Distilled water is taken to prepare Ca2+A concentration of 250mg/L, basicity 250mg/L, Zn2+It is 5mg/L and pH value 9.0 or so
Test water, prepared corrosion inhibiter sample is added thereto, 10h, sampling analysis water are stood in 80 ± 1 DEG C of waters bath with thermostatic control
Middle residue Zn2+Concentration, while doing blank sample, and calculate resistance zinc rate.
Hindering zinc rate calculation formula is：Hinder zinc rate=(C-C0) × 100%/(C1-C0)
C：Survey Zn2+Concentration (mg/L)
C0：The Zn of blank sample2+Concentration (mg/L)
C1：Zn in raw water2+Concentration (mg/L)
(4) measurement of corrosion inhibition
20# quality carbon steel test pieces are fixed on lacing film instrument, are put into the test water added with corrosion inhibiter sample, water quality is shown in
Table 1,45 ± 1 DEG C of steady temperature keep rotating speed 75rpm to rotate 72 hours, and the weight of the front and back test piece of record experiment calculates average corruption
Lose speed.
Average corrosion rate calculation formula is：F=(C × △ W)/(A × T × ρ)
C：Computational constant, with mm/a (millimeter/year) be unit when, C=8.76 × 107
△W：The corrosion weight loss (g) of test specimen
A：Area (the cm of test specimen2)
T：The corrosion test time (h)
ρ：Density (the kg/m of material for test3)
Table 1
The assay method of water quality is with reference to as follows：
Ca2+(with CaCO3Meter, mg/L)：Reference standard GB/T 6910-2006
Total alkalinity is (with CaCO3Meter, mg/L)：Reference standard GB/T 15451-2006；
Total hardness is (with CaCO3Meter, mg/L)：Reference standard GB/T 6909-2008；
Cl-(mg/L)：Reference standard GB/T 15453-2008；
SO4 2-(mg/L)：Reference standard GB/T 14642-2009；
PH value：Reference standard GB/T 6920-1986；
Conductivity (μ s/cm)：Reference standard GB/T 6908-2008；
Total molten solid (mg/L)：Reference standard GB/T 14415-2007.
Table 2
From the data in table 2 can be seen that the present invention copolymer be applied to circulating water treatment to corrosion of carbon steel have compared with
Good remission effect, while there is certain scale inhibition effect.Comparing embodiment 4 and comparative example 1-3 can be seen that according to the present invention
The type of selection monomer could obtain the copolymer haveing excellent performance.
Test case 2
The copolymer and the resistance after other medicaments (antisludging agent and/or dispersant) compounding that this test case is used for illustrating the present invention
Dirty corrosion inhibition.
The water quality for testing raw water is as shown in table 3, and experiment raw water 1 and 2, which is concentrated 5 times, respectively is used as test water 1 and 2, will
Experiment raw water 3 concentrate 3 times and use sulfuric acid adjust test water pH value within the scope of 7.8-8.3 as test water 3.
Table 3
Respectively following compound prescription is added into test water 1,2,3：
Compound prescription 1：Poly-epoxy succinic acid (Active quantities be 40%), embodiment 2 prepare copolymer
(referred to as No. 2), acrylic acid and 2- acrylamide-2-methylpro panesulfonic acids copolymer (abbreviation AA/AMPS, the weight of each structural unit
Amount is than being 7/3, active quantities 30%, and Limiting Viscosity is 0.075dL/g at 30 DEG C), white vitriol, after adding, gather in water
Epoxysuccinic acid, No. 2, AA/AMPS and Zn2+Concentration be respectively 2mg/L, 15mg/L, 2mg/L and 2mg/L.
Compound prescription 2：Poly-aspartate (Active quantities be 40%), embodiment 4 prepare copolymer
(referred to as No. 4), acrylic acid and 2- acrylamide-2-methylpro panesulfonic acids and hydroxypropyl acrylate copolymer (abbreviation AA/AMPS/
HPA, the weight ratio of each structural unit are 14/3/3, active quantities 30%, and Limiting Viscosity is 0.081dL/g at 30 DEG C), seven water
Zinc sulfate, after adding, poly-aspartate, No. 4, AA/AMPS/HPA and Zn in water2+Concentration be respectively 2mg/L, 15mg/L,
2mg/L and 2mg/L.
Comparative formula 1：Poly-epoxy succinic acid, 2- hydroxyethylidene diphosphonic acid guanidine-acetic acids (abbreviation HPAA), AA/AMPS and seven water sulfuric acid
Zinc, after adding, poly-epoxy succinic acid, HPAA, AA/AMPS/HPA and Zn in water2+Concentration be respectively 2mg/L, 15mg/L, 2mg/
L and 2mg/L.
Comparative formula 2：Poly-epoxy succinic acid, sodium molybdate, AA/AMPS and white vitriol, after adding, polycyclic oxygen amber in water
Amber acid, sodium molybdate, AA/AMPS and Zn2+Concentration be respectively 2mg/L, 15mg/L, 2mg/L and 2mg/L.
Comparative formula 3：Poly-epoxy succinic acid, 2- hydroxyethylidene diphosphonic acid guanidine-acetic acids (abbreviation HPAA), AA/AMPS and seven water sulfuric acid
Zinc, after adding, poly-epoxy succinic acid, HPAA, AA/AMPS/HPA and Zn in water2+Concentration be respectively 6mg/L, 15mg/L, 6mg/
L and 3mg/L.
By the above-mentioned test water for having added medicament in standing 10h using volumetric flask method in 80 ± 1 DEG C of waters bath with thermostatic control, wait for cold
But residue Ca in sampling analysis water after2+Concentration, while doing blank sample, and calculate scale inhibition performance, computational methods are the same as test case 1.
20# quality carbon steel test pieces are fixed on lacing film instrument, are put into the above-mentioned test water for having added medicament, constant temperature
Degree is 45 ± 1 DEG C, and it is that 75rpm rotates 72h to keep rotating speed, and the weight of the front and back test piece of record experiment calculates average corrosion rate
(F), computational methods are the same as test case 1.
The measurement result of scale inhibition performance and average corrosion rate is as shown in table 4.
Table 4
As can be seen from Table 4, copolymer of the invention in other corrosion inhibiting and descaling agents for when compounding corrosion inhibiting and descaling agent, throwing
Preferable anticorrosion-antiscaling effect can be still obtained under the conditions of dosage is lower, thus can reduce adding for other corrosion inhibiting and descaling agents
Amount, is adapted to recirculated water system.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (11)
1. application of the copolymer in processing cycle water, which contains the knot that the thiourea derivative shown in formula (I) provides
Structure unit, by C3-10Unsaturated carboxylic acid provide structural unit and by C4-10Acrylate provide structural unit,
Wherein, R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2-10Aliphatic chain, the aliphatic chain be saturation
Or undersaturated and R1、R2、R3And R4At least one of be undersaturated aliphatic chain.
2. application according to claim 1, wherein the unsaturated carboxylic acid be acrylic acid, maleic acid, methacrylic acid and
At least one of methylene-succinic acid.
3. application according to claim 1, wherein the acrylate is alkyl acrylate and/or acrylic acid hydroxyl alkane
Base ester.
4. application according to claim 1, wherein the acrylate is methyl acrylate, ethyl acrylate, acrylic acid
At least one of hydroxyl ethyl ester and hydroxypropyl acrylate.
5. according to the application described in any one of claim 1-4, wherein the unsaturated fatty chain is alkenyl or alkenyl alkane
The aliphatic chain of base, the saturation is alkyl or hydroxyalkyl.
6. according to the application described in any one of claim 1-4, wherein the thiourea derivative is allylthiourea, third
Alkenyl thiocarbamide, N, N'- diallyl -2- thiocarbamides, N, N'- diallyl -2- thiocarbamides,
At least one of N- (2- ethoxys)-N'-2- Allyl thioureas and N- (2- ethoxys)-N'-2- allylthioureas.
7. according to the application described in any one of claim 1-4, wherein the thiourea derivative, unsaturated carboxylic acid and third
The weight ratio of olefin(e) acid ester is 1-6:0.5-5:1.
8. according to the application described in any one of claim 1-3, wherein the viscosity average molecular weigh of the copolymer is
1000-20000。
9. according to the application described in any one of claim 1-3, wherein the viscosity average molecular weigh of the copolymer is
5000-10000。
10. application according to claim 1, wherein the additive amount of the copolymer is 10-100mg/L recirculated waters.
11. the application according to claim 1 or 10, wherein the additive amount of the copolymer is 20-60mg/L recirculated waters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510546239.3A CN106478877B (en) | 2015-08-31 | 2015-08-31 | A kind of copolymer and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510546239.3A CN106478877B (en) | 2015-08-31 | 2015-08-31 | A kind of copolymer and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106478877A CN106478877A (en) | 2017-03-08 |
| CN106478877B true CN106478877B (en) | 2018-08-17 |
Family
ID=58235111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510546239.3A Active CN106478877B (en) | 2015-08-31 | 2015-08-31 | A kind of copolymer and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106478877B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111286312A (en) * | 2020-02-20 | 2020-06-16 | 中国石油天然气股份有限公司 | Slow-release corrosion and scale inhibitor capsule for oil well and preparation method thereof |
| CN114891160B (en) * | 2022-04-28 | 2024-01-30 | 广东深展实业有限公司 | Asparagus resin and epoxy resin modified water-based resin hydroxy acrylic resin and its preparation method and application |
| CN116082542A (en) * | 2022-11-29 | 2023-05-09 | 嘉兴沃特泰科环保科技股份有限公司 | Phosphorus-free corrosion and scale inhibitor and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625930A (en) * | 1967-12-28 | 1971-12-07 | Loctite Corp | Anaerobic composition and process for bonding nonporous surfaces, said composition comprising an acrylic monomer a peroxy initiator and a bonding accelerator |
| US4902765A (en) * | 1988-07-19 | 1990-02-20 | American Cyanamid Company | Allyl thiourea polymers |
| CN1214704A (en) * | 1996-03-28 | 1999-04-21 | Cytec技术有限公司 | Novel polymeric sulfide mineral depressants |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2999917B1 (en) * | 2012-12-26 | 2017-06-23 | Oreal | MOLECULAR FOOTPRINTED POLYMER FOR SELECTIVELY PUSHING ODORANT MOLECULES |
-
2015
- 2015-08-31 CN CN201510546239.3A patent/CN106478877B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625930A (en) * | 1967-12-28 | 1971-12-07 | Loctite Corp | Anaerobic composition and process for bonding nonporous surfaces, said composition comprising an acrylic monomer a peroxy initiator and a bonding accelerator |
| US4902765A (en) * | 1988-07-19 | 1990-02-20 | American Cyanamid Company | Allyl thiourea polymers |
| CN1214704A (en) * | 1996-03-28 | 1999-04-21 | Cytec技术有限公司 | Novel polymeric sulfide mineral depressants |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106478877A (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106478877B (en) | A kind of copolymer and the preparation method and application thereof | |
| CN101280518B (en) | Alkali-resistant sequestering dispersant and preparation thereof | |
| CN105984964B (en) | A kind of phosphate-free water treatment agent and the preparation method and application thereof | |
| CN106478872B (en) | A kind of copolymer and the preparation method and application thereof | |
| CN106478873B (en) | A kind of copolymer and the preparation method and application thereof | |
| CN104119483B (en) | A kind of preparation method of modified acrylate emulsion | |
| CN106478879B (en) | A kind of copolymer and the preparation method and application thereof | |
| CN103833150B (en) | For the dirt dispersion agent and preparation method thereof of recirculating cooling water system | |
| CN106478876B (en) | A kind of copolymer and the preparation method and application thereof | |
| CN103897115B (en) | Terpolymer as concrete workability improver | |
| CN109879451B (en) | Preparation method of copolymer water treatment agent | |
| CN108017163A (en) | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water | |
| CN107828016A (en) | A kind of preparation method of viscosity depressant for drilling fluid | |
| CN103254370B (en) | A kind of waterborne preprinting emulsion and preparation method thereof | |
| CN106430645B (en) | A kind of composite slow-corrosion scale resistor and its application | |
| CN105984965B (en) | A kind of phosphate-free water treatment agent and the preparation method and application thereof | |
| CN106478874B (en) | A kind of copolymer and the preparation method and application thereof | |
| CN116462802A (en) | Environment-friendly scale inhibition dispersing agent and preparation method thereof | |
| CN105441951B (en) | A kind of metal-polishing liquid and preparation method thereof | |
| CN108328753A (en) | A kind of fluorescent tracing type antisludging agent and its preparation method and application | |
| CN108192099A (en) | Poly-aspartate/tryptamines graft copolymer and its synthetic method | |
| CN105152565B (en) | Polyphosphonic acid type water reducing agents and synthesis method thereof | |
| CN107522303A (en) | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water | |
| CN111072164B (en) | Composite scale and corrosion inhibitor and application thereof in medium and hard water | |
| CN107779135A (en) | A kind of good water-borne pressure sensitive adhesive of the low stability of cost |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |