CN106478877A - A kind of copolymer and preparation method and application - Google Patents
A kind of copolymer and preparation method and application Download PDFInfo
- Publication number
- CN106478877A CN106478877A CN201510546239.3A CN201510546239A CN106478877A CN 106478877 A CN106478877 A CN 106478877A CN 201510546239 A CN201510546239 A CN 201510546239A CN 106478877 A CN106478877 A CN 106478877A
- Authority
- CN
- China
- Prior art keywords
- copolymer
- solution
- acid
- monomer
- water
- 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.)
- Granted
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)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to chemical field, disclose a kind of copolymer, this copolymer contains the construction unit that thiourea derivative shown in formula (I) provides, by C3-10Unsaturated carboxylic acid provide construction unit and by C4-10Acrylate provide construction unit, wherein, R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2-10Aliphatic chain and therein at least one be undersaturated aliphatic chain.The invention also discloses the preparation method of described copolymer, including：At 50-95 DEG C, monomer, initiator and molecular weight regulator are mixed, then continued reaction 1-4h at 75-95 DEG C.The invention also discloses the prepared copolymer of methods described and its application 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 copolymer and preparation method and application, in particular it relates to a kind of copolymer,
The application in circulating water treatment of the preparation method of copolymer and this copolymer.
Background technology
At present, corrosion inhibiting and descaling agent is added to remain control metal erosion and fouling in recirculating cooling water system
Common method.Phosphorus system water treatment agent because it is nontoxic, at a low price and the inhibition that had and scale-inhibiting properties, mesh
Front still account for definitely leading status in water process.On the one hand, it is the corruption solving industrial circulating water system
Erosion and scale problems have made huge positive contribution；On the other hand, because phosphorus system water treatment agent can give work
Industry waste water brings substantial amounts of phosphorus-containing compound, causes the pollution of environment, the others thus people begin one's study
" green product " is substituting it.In general, corrosion-mitigation scale-inhibition agent prescription is by inhibition component and antiscaling dispersion
Component two parts form.The excellent without phosphorus copolymer analog dirt dispersion agent kind of scale-inhibiting properties is more, wherein
A lot of successful Application in actual production.And the optional leeway of non-phosphate inhibitor of function admirable is less,
Over more than 30 year, new non-phosphate inhibitor still in positive exploration among, early 1990s by
The U.S. exploitation green corrosion inhibitor poly-aspartate and poly-epoxy succinic acid, all can directly biodegradation, right
Water nonpollution, by water treatment field extensive attention although they possess certain corrosion inhibition,
But it is not the corrosion inhibiter of function admirable.In addition in organic amine corrosion inhibiter, imidazoline corrosion inhibitor, sky
So corrosion inhibiter is modified has been also carried out numerous studies with aspects such as Compositional type non-phosphate inhibitors, and corrosion mitigating effect is all not
The corrosion mitigating effect of phosphorus family corrosion inhibitor can be reached, due to factors such as cost, consumption, technical problems, in industry
All do not applied on a large scale in production.
CN 103627235A discloses a kind of acrylic acid antirusting paint, and it contains following raw materials：Acrylic acid
Resin, cellulose acetate, allylthiourea, epoxy resin, aluminium oxide, tributyl phosphate, cerium oxide,
Politef, triethanolamine, citric acid hydrazine and iron oxide red.
CN1103343C discloses and suppresses sulfide ore during froth flotation Ore to have reclaimed valency
The inhibitor of the novelty of Ore and in foam flotation method using the method for this inhibitor.Novel suppression
Agent is the terpolymer of (methyl) acrylamide, allylthiourea and (methyl) hydroxyalkyl acrylates.
But above two is not appropriate for being used as the resistance of recirculated water using the polymer that thiourea derivative obtains
Dirty corrosion inhibiter.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, provides a kind of new copolymer and its preparation side
Method and application.
The present inventor research find, by the thiourea derivative containing unsaturated bond, unsaturated carboxylic acid and
The polymer of acrylic ester copolymer gained is used for circulating water treatment, right in the case of not introducing containing phosphorus component
Corrosion of carbon steel has preferable corrosion mitigating effect, has certain scale inhibition effect simultaneously.
Therefore, to achieve these goals, in a first aspect, the invention provides a kind of copolymer, this is altogether
Polymers contains the construction unit that thiourea derivative shown in formula (I) provides, by C3-10Unsaturated carboxylic
Acid provide construction unit and by C4-10Acrylate provide construction unit,
Wherein, R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2-10Aliphatic chain,
Described aliphatic chain is saturation or undersaturated and R1、R2、R3And R4At least one of for undersaturated
Aliphatic chain.
Second aspect, the invention provides the preparation method of the copolymer described in first aspect, the method bag
Include：At 50-95 DEG C, monomer, initiator and molecular weight regulator are mixed, then at 75-95 DEG C
Lower continuation reaction 1-4h, wherein, described monomer includes thiourea derivative, unsaturated carboxylic acid and acrylate.
The third aspect, the invention provides the copolymer that the method described in second aspect is obtained.
Fourth aspect, the invention provides the copolymer described in first aspect or the third aspect is in processing cycle
Application in water.
During circulating water treatment, the copolymer using the present invention can obtain preferable corrosion mitigating effect, simultaneously
Also it is obtained in that preferable resistance calcium carbonate scale and steady zinc effect.The present invention can be in the bar without phosphorous medicament
Preferable corrosion mitigating effect is obtained under part, environmentally friendly and there is 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 embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, in the case of illustrating on the contrary, the term " limiting viscosity " of use refers to
The contribution to solution viscosity for the individual molecule, is the viscosity of reflection polymer characteristicses, and its value does not become with concentration,
Unit is deciliter/gram (dL/g), and limiting viscosity is often used as measuring of molecular weight, is generally glued with capillary tube
Degree meter (as Ubbelohde viscometer) records；Unless stated otherwise (as embodiment), it is related in the present invention
Content or weight are all in terms of effective content (content of solute or weight).
The copolymer that the present invention provides contain the construction unit that thiourea derivative shown in formula (I) provides,
By C3-10(as C3、C4、C5、C6、C7、C8、C9、C10) unsaturated carboxylic acid provide structure
Unit and by C4-10(as C4、C5、C6、C7、C8、C9、C10) acrylate provide structure
Unit,
Wherein, R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2-10(as C2、C3、
C4、C5、C6、C7、C8、C9、C10) aliphatic chain, described aliphatic chain be saturation or undersaturated and
R1、R2、R3And R4At least one of be undersaturated aliphatic chain.Preferably, the copolymerization of the present invention
Thing not phosphorous (element).
Wherein, described unsaturated carboxylic acid can be for double bond containing carboxylic acid it is preferable that described unsaturated carboxylic acid
For at least one in acrylic acid, maleic acid, methacrylic acid and methylene-succinic acid.Described acrylic acid
Ester can be for alkyl acrylate and/or acrylic acid hydroxy alkyl ester it is preferable that described acrylate be propylene
At least one in sour methyl ester, ethyl acrylate, 2-(Acryloyloxy)ethanol and Hydroxypropyl acrylate.
Preferably, described unsaturated fatty chain is thiazolinyl or alkenylalkyl (as pi-allyl or acrylic),
The aliphatic chain of described saturation is alkyl or hydroxyalkyl (as ethoxy).It is highly preferred that described thiourea derives
Thing is allylthiourea, Allyl thiourea, N, N'- diallyl -2- thiourea, N, N'- diallyl -2- sulfur
In urea, N- (2- ethoxy)-N'-2- Allyl thiourea and N- (2- ethoxy)-N'-2- allylthiourea at least
A kind of.
According to the present invention, the weight ratio of described thiourea derivative, unsaturated carboxylic acid and acrylate is preferably
1-6:0.5-5:1.This weight is than with preparing monomer " thiourea derivative, the unsaturated carboxylic that copolymer is used
Weight between acid and acrylate " ratio characterizes.
According to the present invention, the limiting viscosity of described copolymer is preferably 0.05-0.2dL/g, more preferably
0.08-0.16dL/g.The viscosity-average molecular weight of described copolymer is preferably 1000-20000, more preferably
5000-10000.
According to the preferred embodiment of the present invention, described copolymer is made up of said structure unit.
The preparation method of the copolymer that the present invention provides includes：At 50-95 DEG C, by monomer, initiator
Mixed with molecular weight regulator, then continued reaction 1-4h, wherein, described monomer at 75-95 DEG C
Including thiourea derivative, unsaturated carboxylic acid and acrylate.
In the present invention, the consumption as the thiourea derivative of monomer, unsaturated carboxylic acid and acrylate and tool
Body selects all as it was previously stated, will not be described here.
According to the preferred embodiment of the present invention, the mode of described mixing is：
A the solution of the solution of monomer and initiator is dropped in the solution of molecular weight regulator by () respectively,
Or
B the solution of the solution of monomer and molecular weight regulator is dropped in the solution of initiator by () respectively,
Or
C () drops to the solution of initiator in molecular weight regulator and the mixed solution of monomer.
In the mode (a), (b) or (c) of mixing, rate of addition is not particularly required.Example
As, in mode (a), the rate of addition of the solution of monomer is 30-400mL/h, the solution of initiator
Rate of addition is 5-120mL/h.In mode (b), the rate of addition of the solution of monomer is 30-400mL/h,
The rate of addition of the solution of molecular weight regulator is 5-120mL/h.In mode (c), the solution of initiator
Rate of addition be 5-120mL/h.
It should be strongly noted that dividing in the mixed solution of mode (c) middle-molecular-weihydroxyethyl regulator and monomer
The concentration of son amount regulator can be 5-85g/L.Mode (c) middle-molecular-weihydroxyethyl regulator and the mixing of monomer
In solution, the concentration of monomer can be 0.25-0.7kg/L.
In a preferred embodiment of the invention, the mode of described mixing is：By the solution of monomer and initiation
The solution of agent drops in the solution of molecular weight regulator respectively.In this preferred implementation, to monomer
Solution and initiator solution rate of addition particularly require it is contemplated that obtain scale inhibitor
Can more preferably copolymer, it is highly preferred that the rate of addition of the solution of monomer is 30-400mL/h, further
It is preferably 60-200mL/h.It is highly preferred that the rate of addition of the solution of initiator is 5-120mL/h, enter
One step is preferably 15-100mL/h.
In a preferred embodiment of the invention, at 50-95 DEG C, by monomer, initiator and molecular weight
The mode that regulator is mixed is preferably the mode of Deca.Can be (excellent to be warming up to 75-95 DEG C in Deca
Elect 80-90 DEG C as) it is also possible to directly carry out Deca at a temperature of 75-95 DEG C (preferably 80-90 DEG C).
In mode (a) as a example it is specifically described below：The solution of the solution of monomer and initiator is dripped respectively
The mode in the solution of molecular weight regulator that adds to can be (specifically, the Ke Yi that heats up in Deca
Start Deca when 50-70 DEG C, then heat up in Deca, cause the temperature of reaction system after completion of dropwise addition
Reach 75-95 DEG C (preferably 80-90 DEG C)) or directly at 75-95 DEG C (preferably 80-90 DEG C)
At a temperature of carry out Deca.In the case of preferred, by the way of heating up while in Deca.
In a preferred embodiment of the invention, described monomer include thiourea derivative, unsaturated carboxylic acid and
Acrylate, the solution of described monomer can be the solution of thiourea derivative, the solution of unsaturated carboxylic acid and
The solution (independent Deca during use) of acrylate or thiourea derivative, unsaturated carboxylic acid and
The mixed solution (during use, three being configured to after mixed solution Deca together) of acrylate.Preferably feelings
Under condition, using the mixed solution of monomer (thiourea derivative, unsaturated carboxylic acid and acrylate), more excellent
Selection of land, the concentration of the mixed solution of described monomer is 0.3-1kg/L.It is well known by those skilled in the art that
The solution of unsaturated carboxylic acid can be obtained after the anhydride of unsaturated carboxylic acid is mixed with solvent it is clear that acid
Acid anhydride using also within the scope of the invention, will not be described in detail herein.
In the present invention, described initiator can be with conventional consumption using it is preferable that described initiator
Consumption is the 2-12% of the total consumption of monomer.The concentration of the solution of described initiator can be 20-720g/L.
In the present invention, the species of described initiator is not particularly required, can make for this area routine
Various radical initiators are it is preferable that described initiator is (water solublity) persulfate, more excellent
Elect at least one in Ammonium persulfate., potassium peroxydisulfate and sodium peroxydisulfate, more preferably Ammonium persulfate. as.
In the present invention, described molecular weight regulator can be according to conventional consumption using it is preferable that described
The consumption of molecular weight regulator is the 2-12% of the total consumption of monomer.The solution of described molecular weight regulator dense
Degree can be 20-720g/L.
In the present invention, to the species of described molecular weight regulator, there is no particular limitation, can be this area
The conventional various materials (reducing agent) with reproducibility are it is preferable that described molecular weight regulator is (water
Dissolubility) sulphite, (water solublity) pyrosulfite and (water solublity) C3-C6Alkanol at least
One kind, more preferably sodium sulfite, Potassium acid sulfite, sodium pyrosulfite, potassium metabisulfite and isopropyl
At least one (most preferably a kind of) in alcohol, more preferably sodium sulfite.Wherein, (water solublity)
C3-C6Alkanol be preferably saturated alkoxides, such as C3、C4、C5Or C6Saturated alkoxides.
Present invention also offers the copolymer being obtained by said method.The limit of the copolymer that the present invention obtains
Viscosity, in the range of 0.05-0.2dL/g (preferably 0.08-0.16dL/g), has excellent scale inhibitor
Can, can use as corrosion inhibiter.
Additionally, present invention also offers the copolymer (as non-phosphate inhibitor) of the invention described above is being processed
Application in recirculated water.Wherein, the addition of described copolymer is preferably 10-100mg/L recirculated water,
More preferably 20-60mg/L recirculated water.
The copolymer of the present invention can be with existing various antisludging agents (as poly-aspartate, poly- epoxy succinic
Acid) and dispersant (as sulfonic acid base co-polymer, carboxylic acid group polymer) use cooperatively, due to the present invention's
Copolymer has preferable anticorrosion-antiscaling property, and it can reduce the use of antisludging agent and dispersant when using
Amount.In the copolymer using the present invention, total consumption of described antisludging agent and dispersant can be than conventional
The low 40-70% of consumption.
Hereinafter will be described the present invention by embodiment.In the following Examples and Comparative Examples,
Allylthiourea, Allyl thiourea, N, N'- diallyl -2- thiourea and N- (2- ethoxy)-N'-2- propylene
Base thiourea is purchased from lark prestige Science and Technology Ltd., and effective content is 98 weight %；Ammonium persulfate.,
Potassium peroxydisulfate, sodium peroxydisulfate, sodium pyrosulfite, sodium sulfite, isopropanol are purchased from Beijing chemistry examination
Agent company, analysis is pure；Acrylic acid is purchased from Tianjin and recovers fine chemistry industry academy, and analysis is pure；Maleic anhydride
Purchased from Beijing Yili Fine Chemicals Co., Ltd., analyze pure；Methacrylic acid and methylene-succinic acid purchase
From Shanghai Yi Kang chemical materialss company limited；Acrylic acid methyl ester., ethyl acrylate, 2-(Acryloyloxy)ethanol and
Hydroxypropyl acrylate is purchased from lark prestige Science and Technology Ltd., and effective content is all not less than 99 weight %.
In embodiment and comparative example, the assay method of solid content is as follows：
Weigh about 1.0g about corrosion inhibiter sample, be accurate to 0.0002g, be placed in the flat tared dish weighed
In, careful shake makes medicament natural flow, forms one layer of uniform thin film in ware bottom, is then placed in electric heating
In drying baker, begin to warm up from room temperature, after 4h being dried at 120 DEG C, weigh once every half an hour
Until constant weight.Take out after constant weight, put in exsiccator and be cooled to room temperature, weigh.
Solid content computing formula is：Solid content=[(m2-m1)/m] × 100%
m2：Dried medicament and tared dish weight, g
m1：Tared dish net weight, g
m：Weigh the quality of medicament, g
Embodiment 1
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 7.2g and 20ml water, start stirring, so that sodium pyrosulfite is fully dissolved.In a perseverance
Allylthiourea 24.5g, methylene-succinic acid 18g, acrylic acid methyl ester. 18g is added in pressure Dropping funnel
With 100ml water, shake up；Add Ammonium persulfate. 1.2g and 40ml water in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start the liquid in two constant pressure funnels of Deca
Body, continues to rise high-temperature to 80 DEG C simultaneously, controls rate of addition to make the liquid in two constant pressure funnels
It is added dropwise to complete in 1 hour, continues insulation reaction 2 hours afterwards, stop test, cool down to obtain product,
The solid content of product is 29.4%.
Embodiment 2
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Potassium peroxydisulfate 2.4g and 40ml water, start stirring, so that potassium peroxydisulfate is fully dissolved.Drip in a constant voltage
Allyl thiourea 27.6g, maleic anhydride 21g, ethyl acrylate 12g and 100ml is added in liquid funnel
Water, shakes up；Add sodium sulfite 6g and 20ml water in another constant pressure funnel, shake up；
Start to warm up, when temperature is increased to 60 DEG C, start the liquid in two constant pressure funnels of Deca, with
Shi Jixu rises high-temperature to 75 DEG C, controls rate of addition to make liquid in two constant pressure funnels 1.5
It is added dropwise to complete in individual hour, continues insulation reaction 2 hours afterwards, stop test, cool down to obtain product, produce
The solid content of product is 30.1%.
Embodiment 3
Lower in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer plus
Enter isopropanol 4.8g and 20ml water, start stirring.Allyl sulfide is added in a constant pressure funnel
Urea 30.6g, methacrylic acid 24g, 2-(Acryloyloxy)ethanol 6.1g and 100ml water, shake up；Another
Add sodium peroxydisulfate 3.6g and 40ml water in individual constant pressure funnel, shake up；Start to warm up, work as temperature
When being increased to 70 DEG C, start the liquid in two constant pressure funnels of Deca, continue to rise high-temperature extremely simultaneously
95 DEG C, rate of addition is controlled so that the liquid in two constant pressure funnels is added dropwise to complete in 0.5 hour,
Continue insulation reaction afterwards to stop after 1 hour testing, cool down to obtain product, the solid content of product is 30.5%.
Embodiment 4
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 3.6g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
Allylthiourea 33.7g, acrylic acid 18g, Hydroxypropyl acrylate 9.2g and 100ml is added in pressure Dropping funnel
Water, shakes up；Add Ammonium persulfate. 4.8g and 40ml water in another constant pressure funnel, shake up；
Start to warm up, when temperature is increased to 50 DEG C, start the liquid in two constant pressure funnels of Deca, control
Rate of addition processed makes the liquid in two constant pressure funnels be added dropwise to complete in 1.5 hours, continues simultaneously
Continue and be warming up to 85 DEG C, continue insulation reaction 3 hours afterwards, stop test, cool down to obtain product, product
Solid content is 31.1%.
Embodiment 5
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 2.4g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
Pressure Dropping funnel in add allylthiourea 36.3g, methacrylic acid 18g, acrylic acid methyl ester. 6g and
100ml water, shakes up；Add Ammonium persulfate. 6g and 40ml water in another constant pressure funnel, shake
Even；Start to warm up, when temperature is increased to 65 DEG C, start the liquid in two constant pressure funnels of Deca,
Control rate of addition so that the liquid in two constant pressure funnels is added dropwise to complete in 1 hour, continue simultaneously
High-temperature of continuing rising, to 90 DEG C, continues insulation reaction 3 hours afterwards, stops test, cools down to obtain product, produces
The solid content of product is 29.8%.
Embodiment 6
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 1.2g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
N, N'- diallyl -2- thiourea 24.5g, acrylic acid 30g, Hydroxypropyl acrylate is added in pressure Dropping funnel
6.1g and 100ml water, shakes up；Sodium peroxydisulfate 7.2g and 40ml is added in another constant pressure funnel
Water, shakes up；Start to warm up, when temperature is increased to 50 DEG C, start in two constant pressure funnels of Deca
Liquid, control rate of addition so that the liquid in two constant pressure funnels is added dropwise to complete in 2 hours,
Continue to rise high-temperature to 90 DEG C simultaneously, continue insulation reaction 4 hours afterwards, stop test, cool down and must produce
Product, the solid content of product is 30.6%.
Embodiment 7
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 4.8g and 20ml water, start stirring, so that sodium pyrosulfite is fully dissolved.In a perseverance
Pressure Dropping funnel in add N- (2- ethoxy)-N'-2- Allyl thiourea 27.6g, maleic anhydride 24g, third
Olefin(e) acid ethyl ester 9g and 100ml water, shake up；Ammonium persulfate. 2.4g is added in another constant pressure funnel
With 40ml water, shake up；Start to warm up, when temperature is increased to 55 DEG C, starts two constant voltages of Deca and drip
Liquid in liquid funnel, controls rate of addition to make the liquid in two constant pressure funnels in 2 hours
It is added dropwise to complete, continue to rise high-temperature to 85 DEG C simultaneously, continue insulation reaction 2 hours afterwards, stop test,
Cool down to obtain product, the solid content of product is 30.7%.
Embodiment 8
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 5.6g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
Allyl thiourea 24.5g, methylene-succinic acid 27g, 2-(Acryloyloxy)ethanol 9g is added in pressure Dropping funnel
With 100ml water, shake up；Add potassium peroxydisulfate 3.6g and 40ml water in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 70 DEG C, start simultaneously in two constant pressure funnels of Deca
Liquid, control rate of addition so that the liquid in two constant pressure funnels is dripped in 1.5 hours
Become, continue to rise high-temperature to 90 DEG C simultaneously, continue insulation reaction 2 hours afterwards, stop test, cooling
Obtain product, the solid content of product is 29.8%.
Embodiment 9
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 1.2g, allylthiourea 30.6g, maleic anhydride 18g, Hydroxypropyl acrylate 12g and
120ml water, starts stirring, so that each material is fully dissolved.Over cure is added in a constant pressure funnel
Sour ammonium 1.2g and 25ml water, shake up；Start to warm up, when temperature is increased to 60 DEG C, starts simultaneously at and drip
Plus the liquid in constant pressure funnel, control rate of addition to make the liquid in constant pressure funnel at 1.5
It is added dropwise to complete in hour, continue to rise high-temperature to 80 DEG C simultaneously, continue insulation reaction 2 hours afterwards, stop
Only test, cool down to obtain product, the solid content of product is 29.7%.
Embodiment 10
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 7.2g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
Allylthiourea 36.7g, acrylic acid 12g, acrylic acid methyl ester. 12g and 110ml is added in pressure Dropping funnel
Water, shakes up；Add Ammonium persulfate. 7.2g and 40ml water in another constant pressure funnel, shake up；
Start to warm up, when temperature is increased to 50 DEG C, start simultaneously at the liquid in two constant pressure funnels of Deca,
Rate of addition is controlled so that the liquid in two constant pressure funnels is added dropwise to complete in 1.5 hours, simultaneously
Continue to rise high-temperature to 95 DEG C, continue insulation reaction 3 hours afterwards, stop test, cool down to obtain product,
The solid content of product is 30.4%.
Embodiment 11
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 6g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a constant voltage
In Dropping funnel add Allyl thiourea 30.6g, maleic anhydride 12g, Hydroxypropyl acrylate 18.4g and
100ml water, shakes up；Add Ammonium persulfate. 3.6g and 40ml water in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 60 DEG C, start the liquid in two constant pressure funnels of Deca
Body, controls rate of addition so that the liquid in two constant pressure funnels is added dropwise to complete in 1.5 hours,
Continue to rise high-temperature to 80 DEG C simultaneously, continue insulation reaction 2 hours afterwards, stop test, cool down and must produce
Product, the solid content of product is 29.7%.
Embodiment 12
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 2.4g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
Pressure Dropping funnel in add allylthiourea 27.6g, acrylic acid 15g, Hydroxypropyl acrylate 18.4g and
100ml water, shakes up；Add Ammonium persulfate. 7.2g and 40ml water in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start simultaneously in two constant pressure funnels of Deca
Liquid, control rate of addition so that the liquid in two constant pressure funnels is dripped in 1.5 hours
Become, continue to rise high-temperature to 95 DEG C simultaneously, continue insulation reaction 3 hours afterwards, stop test, cooling
Obtain product, the solid content of product is 30.4%.
Comparative example 1
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 3.6g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
Add acrylic acid 40g, Hydroxypropyl acrylate 20.4g and 100ml water in pressure Dropping funnel, shake up；?
Add Ammonium persulfate. 4.8g and 40ml water in another constant pressure funnel, shake up；Start to warm up, when
When temperature is increased to 50 DEG C, start the liquid in two constant pressure funnels of Deca, control rate of addition to make
Liquid in two constant pressure funnels is added dropwise to complete in 1.5 hours, is continuously heating to 85 DEG C simultaneously,
Continue insulation reaction 3 hours afterwards, stop test, cool down to obtain product, the solid content of product is 30.6%.
Comparative example 2
Method according to embodiment 4 prepares copolymer, except for the difference that, replaces " third with " acrylamide "
Olefin(e) acid ", the solid content of the product obtaining is 30.1%.
Comparative example 3
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 3.6g and 20ml water, start stirring, so that sodium sulfite is fully dissolved.In a perseverance
Add allylthiourea 47.9g, Hydroxypropyl acrylate 13.32g and 100ml water in pressure Dropping funnel, shake
Even；Add Ammonium persulfate. 4.8g and 40ml water in another constant pressure funnel, shake up；Start to rise
Temperature, when temperature is increased to 50 DEG C, starts the liquid in two constant pressure funnels of Deca, controls Deca
Speed makes the liquid in two constant pressure funnels be added dropwise to complete in 1.5 hours, continues to heat up simultaneously
To 85 DEG C, continue insulation reaction 3 hours afterwards, stop test, cool down to obtain product, the solid content of product
For 30.6%.
Test case 1
This test case is used for the performance of the copolymer obtained by above-described embodiment and comparative example is described.
Measure the limiting viscosity of the copolymer of each embodiment and comparative example acquisition respectively in accordance with the following methods
And anticorrosion-antiscaling property, test Chinese medicine dosage and be 10mg/L, result is as shown in table 2, table 2
In, "/" represents and is not measured.
(1) mensure of limiting viscosity
Take corrosion inhibiter sample in culture dish, with the pH of 80g/L sodium hydroxide solution adjusting sample solution
It is worth to 9.0, is then placed in baking oven toasting 4h when 120 ± 2 DEG C, taking-up is placed in exsiccator and is cooled to
Room temperature, that is, make and sample be dried.Weigh 0.27g and sample is dried, be accurate to 0.0002g, in beaker,
After the dissolving of 101g/L sodium thiocyanate solution, it is transferred in 50mL volumetric flask, fixed with sodium thiocyanate solution
Hold to scale, shake up, test solution.This liquid is added clean dried through G3 acidproof filtration funnel
Ubbelohde viscometer in, to filling between graticule G, H, constant temperature 10～15min, with rubber pipette bulb will
Test solution sucks more than C ball graticule E, even if reading, with stopwatch, the time that test solution flows out graticule E, F, even
Continue and measure three times, error is less than 0.2s, takes its meansigma methods ts.Carry out the sky of sodium thiocyanate solution simultaneously
White experiment t0s.
Limiting viscosity computing formula is：Limiting viscosity={ 2 [(t/t0-1)-㏑t/t0]}1/2/C
t0：Sodium thiocyanate solution flows through the time of viscometer graticule E, F, s
t：Test solution flows through the time of viscometer graticule E, F, s
C：The concentration of test solution, g/dL
(2) hinder the mensure of calcium carbonate scale performance
Distilled water is taken to prepare Ca2+Concentration is 600mg/L, basicity is 600mg/L, pH value 9.0 about
Test water, the corrosion inhibiter preparing sample is added thereto, in 80 ± 1 DEG C of waters bath with thermostatic control stand
10h, remaining Ca in sample analysis water2+Concentration, do blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is：Scale inhibition performance=(C-C0) × 100%/(C1-C0)
C：Actual measurement Ca2+Concentration (mg/L)
C0：The Ca of blank sample2+Concentration (mg/L)
C1：Ca in raw water2+Concentration (mg/L)
(3) stablize the mensure of zinc salt performance
Distilled water is taken to prepare Ca2+Concentration is 250mg/L, basicity is 250mg/L, Zn2+For 5mg/L and
PH value, in 9.0 about test water, the corrosion inhibiter preparing sample is added thereto, in 80 ± 1 DEG C
Standing 10h in water bath with thermostatic control, remaining Zn in sample analysis water2+Concentration, do blank sample simultaneously, and count
Calculate resistance zinc rate.
Hindering zinc rate computing formula is：Resistance zinc rate=(C-C0) × 100%/(C1-C0)
C：Actual measurement Zn2+Concentration (mg/L)
C0：The Zn of blank sample2+Concentration (mg/L)
C1：Zn in raw water2+Concentration (mg/L)
(4) mensure of corrosion inhibition
20# quality carbon steel test piece is fixed on lacing film instrument, puts into the test water added with corrosion inhibiter sample
In, water quality is shown in Table 1,45 ± 1 DEG C of steady temperature, keeps rotating speed 75rpm to rotate 72 hours, record examination
Test the weight of before and after's test piece, calculate average corrosion rate.
Average corrosion rate computing formula is：F=(C × △ W)/(A × T × ρ)
C：Computational constant, during with mm/a (millimeter/year) for unit, C=8.76 × 107
△W：The corrosion weight loss (g) of test specimen
A：Area (the cm of test specimen2)
T：Corrosion testing 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；
Electrical conductivity (μ s/cm)：Reference standard GB/T 6908-2008；
Always molten solid (mg/L)：Reference standard GB/T 14415-2007.
Table 2
The copolymer that data from table 2 can be seen that the present invention is applied to circulating water treatment to carbon steel corruption
Erosion has preferable remission effect, has certain scale inhibition effect simultaneously.Comparing embodiment 4 and comparative example
1-3 can be seen that the copolymer that could obtain excellent performance according to the species that the present invention selects monomer.
Test case 2
This test case is used for the copolymer of the present invention and other medicaments (antisludging agent and/or dispersant) are described
Anticorrosion-antiscaling property after compounding.
The water quality of test raw water as shown in table 3, will be tested raw water 1 and 2 respectively and concentrate 5 times as test
With water 1 and 2, test raw water 3 is concentrated 3 times and adjusts the pH value of test water in 7.8-8.3 with sulphuric acid
In the range of as test water 3.
Table 3
Add following compound prescription in test water 1,2,3 respectively：
Compound prescription 1：Poly-epoxy succinic acid (Active quantities are 40%), embodiment 2 makes
Standby copolymer (referred to as No. 2), acrylic acid and the (letter of 2- acrylamide-2-methylpro panesulfonic acid copolymer
Claim AA/AMPS, for 7/3, active quantities are 30% to the weight of each construction unit ratio, limit when 30 DEG C
Viscosity number be 0.075dL/g), zinc sulphate heptahydrate, after adding, poly-epoxy succinic acid, No. 2, AA/AMPS in water
And Zn2+Concentration be respectively 2mg/L, 15mg/L, 2mg/L and 2mg/L.
Compound prescription 2：Poly-aspartate (Active quantities are 40%), embodiment 4 makes
Standby copolymer (referred to as No. 4), acrylic acid and 2- acrylamide-2-methylpro panesulfonic acid and acrylic acid hydroxyl
(abbreviation AA/AMPS/HPA, than for 14/3/3, activity contains methacrylate-trimethoxysilyl propylmethacrylate copolymer for the weight of each construction unit
Measure as 30%, when 30 DEG C, Limiting Viscosity is 0.081dL/g), zinc sulphate heptahydrate, after adding, poly- sky in water
Winter propylhomoserin, No. 4, AA/AMPS/HPA and Zn2+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 acid (abbreviation HPAA), AA/AMPS
And zinc sulphate heptahydrate, 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 zinc sulphate heptahydrate, add
Afterwards, poly-epoxy succinic acid, sodium molybdate, AA/AMPS and Zn in water2+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 acid (abbreviation HPAA), AA/AMPS
And zinc sulphate heptahydrate, 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.
The above-mentioned test water having added medicament is adopted volumetric flask method to stand in 80 ± 1 DEG C of waters bath with thermostatic control
10h, remaining Ca in sample analysis water after cooling2+Concentration, do blank sample simultaneously, and calculate scale inhibition
Rate, computational methods are with test case 1.
20# quality carbon steel test piece is fixed on lacing film instrument, puts into the above-mentioned test water having added medicament
In, steady temperature is 45 ± 1 DEG C, keeps rotating speed to rotate 72h for 75rpm, test piece before and after record test
Weight, calculates average corrosion rate (F), computational methods are with 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, when the copolymer of the present invention is used for compounding corrosion inhibiting and descaling agent, slow at other
Still preferable anticorrosion-antiscaling effect can be obtained under conditions of erosion scale inhibitor dosing amount is relatively low, thus can drop
The dosage of other corrosion inhibiting and descaling agents low, is adapted to recirculated water system.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Apply the detail in mode, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment,
In the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary
Repeat, the present invention no longer separately illustrates to various possible compound modes.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it equally should be considered as content disclosed in this invention.
Claims (11)
1. a kind of copolymer, this copolymer contains the structure that the thiourea derivative shown in formula (I) provides
Unit, by C3-10Unsaturated carboxylic acid provide construction unit and by C4-10Acrylate provide knot
Structure unit,
Wherein, R1、R2、R3And R4It is each independently H, substituted or unsubstituted C2-10Aliphatic chain,
Described aliphatic chain is saturation or undersaturated and R1、R2、R3And R4At least one of for undersaturated
Aliphatic chain；Described unsaturated carboxylic acid is preferably acrylic acid, maleic acid, methacrylic acid and methylene fourth two
At least one in acid；Described acrylate be preferably alkyl acrylate and/or acrylic acid hydroxy alkyl ester and
More preferably in acrylic acid methyl ester., ethyl acrylate, 2-(Acryloyloxy)ethanol and Hydroxypropyl acrylate at least
A kind of.
2. copolymer according to claim 1, wherein, described unsaturated fatty chain be thiazolinyl or
Alkenylalkyl, the aliphatic chain of described saturation is alkyl or hydroxyalkyl；Preferably, described thiourea derivative is
Allylthiourea, Allyl thiourea, N, N'- diallyl -2- thiourea, N, N'- diallyl -2- thiourea,
In N- (2- ethoxy)-N'-2- Allyl thiourea and N- (2- ethoxy)-N'-2- allylthiourea at least one
Kind.
3. copolymer according to claim 1, wherein, described thiourea derivative, unsaturated carboxylic
The weight of acid and acrylate ratio is for 1-6:0.5-5:1.
4. the copolymer according to any one in claim 1-3, wherein, described copolymer
Viscosity-average molecular weight be 1000-20000, preferably 5000-10000.
5. a kind of method of the copolymer prepared described in any one in claim 1-4, its feature exists
In the method includes：At 50-95 DEG C, monomer, initiator and molecular weight regulator are mixed,
Continue reaction 1-4h again at 75-95 DEG C, wherein, described monomer includes thiourea derivative, unsaturated carboxylic
Acid and acrylate.
6. method according to claim 5, wherein, the mode of described mixing is：
A the solution of the solution of monomer and initiator is dropped in the solution of molecular weight regulator by () respectively,
Or
B the solution of the solution of monomer and molecular weight regulator is dropped in the solution of initiator by () respectively,
Or
C () drops to the solution of initiator in molecular weight regulator and the mixed solution of monomer.
7. method according to claim 6, wherein, in mode (a), the solution of monomer drip
Acceleration is 30-400mL/h, and the rate of addition of the solution of initiator is 5-120mL/h；Or
In mode (b), the rate of addition of the solution of monomer is 30-400mL/h, molecular weight regulator
The rate of addition of solution is 5-120mL/h；Or
In mode (c), the rate of addition of the solution of initiator is 5-120mL/h.
8. method according to claim 5, wherein, the consumption of described initiator is always used for monomer
The 2-12% of amount；Preferably, described initiator is persulfate, more preferably Ammonium persulfate., persulfuric acid
At least one in potassium and sodium peroxydisulfate.
9. method according to claim 5, wherein, the consumption of described molecular weight regulator is single
The 2-12% of the total consumption of body；Preferably, described molecular weight regulator be sulphite, pyrosulfite and
C3-C6Alkanol at least one, more preferably sodium sulfite, Potassium acid sulfite, pyrosulfurous acid
At least one in sodium, potassium metabisulfite and isopropanol.
10. the copolymer that the method described in any one in claim 5-9 is obtained.
Copolymer described in any one answering in processing cycle water in 11. claim 1-4 and 10
With it is preferable that the addition of described copolymer is 10-100mg/L recirculated water, more preferably 20-60mg/L
Recirculated water.
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 true CN106478877A (en) | 2017-03-08 |
| CN106478877B 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) |
Cited By (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 |
| CN114891160A (en) * | 2022-04-28 | 2022-08-12 | 广东深展实业有限公司 | Asparagus resin and epoxy resin modified waterborne hydroxyl acrylic resin and preparation method and application thereof |
| 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 (4)
| 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 |
| WO2014102077A1 (en) * | 2012-12-26 | 2014-07-03 | L'oreal | Molecularly imprinted polymer for selectively trapping odorous molecules |
-
2015
- 2015-08-31 CN CN201510546239.3A patent/CN106478877B/en active Active
Patent Citations (4)
| 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 |
| WO2014102077A1 (en) * | 2012-12-26 | 2014-07-03 | L'oreal | Molecularly imprinted polymer for selectively trapping odorous molecules |
Cited By (4)
| 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 |
| CN114891160A (en) * | 2022-04-28 | 2022-08-12 | 广东深展实业有限公司 | Asparagus resin and epoxy resin modified waterborne hydroxyl acrylic resin and preparation method and application 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106478877B (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102344522B (en) | Environment-friendly printing platen adhesive emulsion and preparation method thereof | |
| CN104403056B (en) | A kind of high temperature resistant copolymer oil well cement retarder and preparation method thereof | |
| CN106478877A (en) | A kind of copolymer and preparation method and application | |
| CN105984964A (en) | Phosphorus-free water treatment agent, and preparation method and application thereof | |
| CN105502698B (en) | A kind of composite scale-inhibiting corrosion inhibitor and its application in circulating water cooling treatment | |
| CN109748405A (en) | A kind of oil field heat-resistance type Barium/Strontium Sulfate scale preventative and preparation method thereof | |
| CN107522301B (en) | Use of corrosion inhibitors or corrosion inhibitor compositions for inhibiting water corrosion | |
| CN102452721A (en) | Phosphorus-free composite scale-inhibiting corrosion-retarding agent and application thereof in water treatment | |
| CN107522300A (en) | The processing method of corrosion inhibiter and composite corrosion inhibitor and preparation method thereof and its application and recirculated water in aqueous corrosion is suppressed | |
| CN106478873A (en) | A kind of copolymer and preparation method and application | |
| CN106495294B (en) | A kind of corrosion-mitigation scale-inhibition fungicide and preparation method thereof | |
| CN106478872A (en) | A kind of copolymer and preparation method and application | |
| KR20170021225A (en) | New polyelectrolytic polymers, process for their preparation and uses thereof | |
| CN106478876A (en) | A kind of copolymer and preparation method and application | |
| CN103332797A (en) | Circulating cooling water non-phosphorus corrosion and scale inhibitor and application thereof | |
| CN106478879A (en) | A kind of copolymer and preparation method and application | |
| CN105176509A (en) | Oil field neutral antiscale agent for barium sulfate and strontium sulfate scale and preparation method thereof | |
| CN103833150A (en) | Dirt dispersion agent for circulating cooling water system and preparation method of dirt dispersion agent | |
| CN106430645B (en) | A kind of composite slow-corrosion scale resistor and its application | |
| CN103254370B (en) | A kind of waterborne preprinting emulsion and preparation method thereof | |
| CN106478874A (en) | A kind of copolymer and preparation method and application | |
| CN109337021B (en) | Application of fluorescent tracing type itaconic acid-aspartic acid copolymer in preparation of water treatment agent | |
| CN105504135B (en) | The method for preparing acrylic acid and the methyl-propane sulfonic acid copolymer sodium salt derivative of 2 acrylamide 2 | |
| CN104341325A (en) | Unsaturated ester and preparation method thereof | |
| CN106478875A (en) | A kind of copolymer and preparation method and application |
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 |