CN105984964A - Phosphorus-free water treatment agent, and preparation method and application thereof - Google Patents
Phosphorus-free water treatment agent, and preparation method and application thereof Download PDFInfo
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- CN105984964A CN105984964A CN201510054850.4A CN201510054850A CN105984964A CN 105984964 A CN105984964 A CN 105984964A CN 201510054850 A CN201510054850 A CN 201510054850A CN 105984964 A CN105984964 A CN 105984964A
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Abstract
The invention discloses a phosphorus-free water treatment agent, a preparation method for the phosphorus-free water treatment agent, and an application of the phosphorus-free water treatment agent in treatment of circulating water. The phosphorus-free water treatment agent is prepared from dimethyldiallylammonium chloride, unsaturated carboxylic acid and acrylate by polymerization, wherein the phosphorus-free water treatment agent has a limiting viscosity of 0.05 to 0.16 dL/g; the unsaturated carboxylic acid is selected from acrylic acid, maleic acid, methacrylic acid or itaconic acid; and the acrylate is selected from methyl acrylate, ethyl acrylate or hydroxypropyl acrylate. The preparation method for the phosphorus-free water treatment agent comprises the following steps: mixing monomers, an initiator and a molecular weight regulator in a manner of dropwise adding at 50 to 95 DEG C, and after dropwise adding is completed, continuing to carry out a reaction at 75 to 95 DEG C for 1 to 4 h, wherein the monomers are the dimethyldiallylammonium chloride, unsaturated carboxylic acid and acrylate. The phosphorus-free water treatment agent provided by the invention has good scale and corrosion inhibition effects, and has good flocculation effects on suspended matters in the circulating water at the same time.
Description
Technical field
The present invention relates to a kind of phosphate-free water treatment agent and preparation method and application, in particular it relates to a kind of
Phosphate-free water treatment agent, the preparation method of phosphate-free water treatment agent and this phosphate-free water treatment agent are in circulating water treatment
In application.
Background technology
According to the requirement of energy-saving and emission-reduction, increasing Circulating Water Field is by improving the cycles of concentration of recirculated water
Using recycled water to save fresh water as circulating cooling make-up water with a large amount of, the most also problem served by band.?
Cycles of concentration improve while the turbidity of recirculated water is also continuously increased, recycled water water quality is relatively compared with fresh water
Difference, concentrates turbidity in Posterior circle water higher.In recirculated water, turbidity raises, and in water, suspended material is easily following
Formation of deposits dirt in ring water system, colloidal substance can form caking property dirt, promotes dirt deposition and leads
Cause local corrosion.Main by adding antisludging agent respectively, delaying in recirculating cooling water system running at present
Erosion agent, antibacterial control circulating water quality and stablize, and the float in water is not had flocculating sedimentation effect,
Run into the turbidity of recirculated water when raising, often use strengthen blowdown, other filter tank backwash method turbid to reduce
Degree.Strengthening blowdown makes recirculated water cycles of concentration reduce, and rate of water make-up strengthens, and wastes great lot of water resources, increases
Add the usage amount of water treatment agent, increase water processing cost, be unfavorable for energy-saving and emission-reduction and environmental protection.Other filter tank
Backwash has certain effect to the removal of float, but can not remove colloid completely, to less float
Removal effect is poor.Both the above method the most not can solve the Problems of Turbidity of recirculated water.
It addition, phosphorus-containing compound to the pollution of water body and causes body eutrophication problem to make people gradually recognize
Know to the importance controlling phosphorus-containing compound discharge.In world wide, a lot of river, lakes are because arranging
Entering substantial amounts of phosphorus causes aquatic plants growth out of control, and dissolved oxygen in water exhausts, final water quality deterioration, aquatic dynamic
Plant disappeares.Along with the raising of environmental consciousness, environmental regulation the strictest, China's many ground in recent years
Side has begun to limit the use containing phosphorus product, and exploitation the most low-phosphorous, phosphate-free water treatment agent has become as
Study hotspot.
CN102477129A disclose a kind of dimethyl diallyl ammonium chloride, methyl methacrylate,
Acrylamide and acrylic acid copolymer, polymerization process is at room temperature carried out, and product has preferably flocculation
Effect of settling, but it is not suitable for use in antisludging agent or corrosion inhibiter.
Document " dimethyl diallyl ammonium chloride and acrylic acid or 2-(Acryloyloxy)ethanol copolymerization kinetics
Research " (Cao Lina etc., Hebei industrial technology, 27 (5): 288-293,2010) have studied dimethyl
Diallyl ammonium chloride (DMDAAC) respectively with acrylic acid (AA) and 2-(Acryloyloxy)ethanol (HEA)
Aqueous free radical copolymerization, literary composition is introduced polymeric reaction temperature select at 297.15-309.15K
In the range of, initiator system is ammonium persulfate-sodium bisulfite, the polymer limit synthesized under this condition
The higher i.e. molecular weight of viscosity is higher, is not suitable for being used as retarding circulating water scaling corrosion inhibiter.
Document " synthesis of AM-MAA-DMDAAC copolymer and performance " (Wang Zhonghua, chemical science and technology,
9 (1): 15-18,2001) use oxidation-reduction trigger system synthesized acrylamide-methacrylic acid-
Dimethyl diallyl ammonium chloride multiple copolymer, its polyreaction initial temperature is below 60 DEG C, gained
The limiting viscosity of copolymer is above 0.23dL/g, and the copolymer of this limiting viscosity is not suitable for recirculated water
Make antisludging agent or corrosion inhibiter.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of new phosphate-free water treatment agent and
Preparation method and application.
To achieve these goals, first aspect, the invention provides a kind of phosphate-free water treatment agent, this nothing
Phosphorus water treatment agent is obtained by dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and acrylic ester polymerization and institute
The limiting viscosity stating phosphate-free water treatment agent is 0.05-0.16dL/g, and wherein, described unsaturated carboxylic acid is selected from third
Olefin(e) acid, maleic acid, methacrylic acid or methylene-succinic acid, described acrylate selected from acrylic acid methyl ester.,
Ethyl acrylate or Hydroxypropyl acrylate.
Second aspect, the invention provides a kind of method preparing phosphate-free water treatment agent, and the method includes:
At 50-95 DEG C, in the way of dropping, monomer, initiator and molecular weight regulator are mixed, drip
After having added at 75-95 DEG C continue reaction 1-4h, described monomer be dimethyl diallyl ammonium chloride,
Unsaturated carboxylic acid and acrylate, wherein, described unsaturated carboxylic acid is selected from acrylic acid, maleic acid, methyl
Acrylic acid or methylene-succinic acid, described acrylate is selected from acrylic acid methyl ester., ethyl acrylate or propylene
Acid hydroxypropyl acrylate.
The third aspect, the invention provides the phosphate-free water treatment agent prepared by the method described in second aspect.
Fourth aspect, the invention provides the phosphate-free water treatment agent described in first aspect or the third aspect at place
Application in reason recirculated water.
By technique scheme, present invention obtains preferable scale inhibitor effect, simultaneously to recirculated water
In float there is preferable flocculating effect.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention 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 individual molecule contribution to solution viscosity, is the viscosity of reflection polymer characteristics, and its value does not becomes with concentration,
Unit is deciliter/gram (dL/g), and limiting viscosity is often used as measuring of molecular weight, generally glues with capillary tube
Degree meter (such as Ubbelohde viscometer) records.
The phosphate-free water treatment agent that the present invention provides is by dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and third
Olefin(e) acid polyisocyanate polyaddition obtains and the limiting viscosity of described phosphate-free water treatment agent is 0.05-0.16dL/g, is preferably
0.065-0.085dL/g, wherein, described unsaturated carboxylic acid is selected from acrylic acid, maleic acid, methacrylic acid
Or methylene-succinic acid (itaconic acid), described acrylate selected from acrylic acid methyl ester., ethyl acrylate or
Hydroxypropyl acrylate (preferably Hydroxypropyl acrylate).
Preferably, dimethyl diallyl ammonium chloride, unsaturated carboxylic acid with the weight ratio of acrylate are
1:(1-10): (0.1-4.5), more preferably 1:(1.5-8): (0.5-3).
The present invention provide the method preparing phosphate-free water treatment agent include: at 50-95 DEG C, by monomer,
Initiator and molecular weight regulator mix, then continue anti-under 75-95 DEG C (preferably 85-95 DEG C)
Answering 1-4h, described monomer is dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and acrylate, wherein,
Described unsaturated carboxylic acid selected from acrylic acid, maleic acid, methacrylic acid or methylene-succinic acid, described third
Olefin(e) acid ester is selected from acrylic acid methyl ester., ethyl acrylate or Hydroxypropyl acrylate (preferably acrylic acid hydroxypropyl
Ester)；The mode of described mixing is:
A the solution of monomer and the solution of initiator are dropped in the solution of molecular weight regulator by () respectively,
Or
B the solution of monomer and the solution of molecular weight regulator are dropped in the solution of initiator by () respectively,
Or
C the solution of initiator is dropped in the mixed solution of molecular weight regulator and monomer by ().
Preferably, dimethyl diallyl ammonium chloride, unsaturated carboxylic acid with the weight ratio of acrylate are
1:(1-10): (0.1-4.5), more preferably 1:(1.5-8): (0.5-3).
In the present invention, at 50-95 DEG C, carry out monomer, initiator and molecular weight regulator mixing
Mode is the mode of dropping.75-95 DEG C (preferably 85-95 DEG C) can be warming up to dropping limit, limit, it is possible to
Directly to drip at a temperature of 75-95 DEG C (preferably 85-95 DEG C).Below in mode (a)
As a example by be specifically described: the solution of monomer and the solution of initiator are dropped to molecular weight regulator respectively
Solution in mode can be dropping limit, limit heat up (specifically, can start when 50-70 DEG C dropping,
Then heat up in dropping limit in limit, and after causing completion of dropwise addition, the temperature of reaction system reaches 75-95 DEG C (preferably
85-95 DEG C)), it is also possible to for directly dripping at a temperature of 75-95 DEG C (preferably 85-95 DEG C).
Under preferable case, use the mode heated up in dropping limit, limit.
In the present invention, described monomer is dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and acrylate,
The solution of described monomer can be the solution of dimethyl diallyl ammonium chloride, the solution of unsaturated carboxylic acid and
The solution (individually dripping during use) of acrylate, it is also possible to for dimethyl diallyl ammonium chloride, no
Saturated carboxylic acid (drips together with after three being configured to mixed solution during use with the mixed solution of acrylate
Add).Under preferable case, use monomer (dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and propylene
Acid esters) mixed solution, it is highly preferred that the concentration of the mixed solution of described monomer is 0.6-1.2kg/L.
It is well known by those skilled in the art that the solution of unsaturated carboxylic acid can be by by the anhydride of unsaturated carboxylic acid
Obtain after mixing with solvent, do not repeat them here.
In the present invention, described initiator can use with conventional consumption, 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 15-120g/L.
In the present invention, the kind not particularly requirement to described initiator, can be that this area routine makes
Various initiators, it is preferable that described initiator is in Ammonium persulfate., potassium peroxydisulfate and sodium peroxydisulfate
At least one.
In the present invention, described molecular weight regulator can use according to conventional consumption, 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 20-180g/L.
In the present invention, to the kind of described molecular weight regulator, there is no particular limitation, can be this area
Conventional various molecular weight regulators, it is preferable that described molecular weight regulator is sodium pyrosulfite or isopropyl
Alcohol, more preferably sodium pyrosulfite.
In the mode (a), (b) or (c) of mixing, to rate of addition not particularly requirement.Example
As, in mode (a), the rate of addition of the solution of monomer is 25-200mL/h, the solution of initiator
Rate of addition is 30-160mL/h.In mode (b), the rate of addition of the solution of monomer is 25-200mL/h,
The rate of addition of the solution of molecular weight regulator is 20-120mL/h.In mode (c), initiator molten
The rate of addition of liquid is 30-160mL/h.
It should be strongly noted that the mixed solution of mode (c) middle-molecular-weihydroxyethyl regulator and monomer divides
The concentration of son amount regulator can be 7.5-80g/L.Mode (c) middle-molecular-weihydroxyethyl regulator and monomer mixed
Closing the concentration of monomer in solution can be 0.37-0.67kg/L.
In a preferred embodiment of the invention, the mode of described mixing is: by solution and the initiation of monomer
The solution of agent drops in the solution of molecular weight regulator respectively.In this preferred implementation, to monomer
Solution and the rate of addition particularly requirement of solution of initiator, it is contemplated that obtain scale inhibitor
Can more preferably phosphate-free water treatment agent, it is highly preferred that the rate of addition of the solution of monomer is 25-200mL/h.
It is highly preferred that the rate of addition of the solution of initiator is 30-160mL/h.
Present invention also offers the phosphate-free water treatment agent prepared by said method.The without phosphorus water that the present invention obtains
The limiting viscosity of inorganic agent, in the range of 0.05-0.16dL/g (preferably 0.065-0.085dL/g), has
Excellent anticorrosion-antiscaling property.
Additionally, present invention also offers phosphate-free water treatment agent the answering in processing cycle water of the invention described above
With.Wherein, the addition of described phosphate-free water treatment agent is preferably 10-100mg/L recirculated water, more preferably
For 20-60mg/L recirculated water.
Hereinafter will be described the present invention by embodiment.In following example, dimethyl diene
Propyl ammonium chloride is purchased from Beijing Yi Nuokai Science and Technology Ltd., content 60 weight %；Acrylic acid, Malaysia
It is limited that anhydride, methacrylic acid and methylene-succinic acid (itaconic acid) are purchased from traditional Chinese medicines group chemical reagent
Company, analytical pure；Acrylic acid methyl ester., ethyl acrylate, Hydroxypropyl acrylate are purchased from Beijing benefit profit essence
Thin Chemical Company, analytical pure；Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, sodium pyrosulfite,
Isopropanol is purchased from Tianjin recovery fine chemistry industry institute, analytical pure；Poly dimethyl allyl chlorination
Ammonium is purchased from Shandong Lu Yue Chemical Co., Ltd.；Methylene-succinic acid/Hydroxypropyl acrylate and maleic anhydride/the third
Olefin(e) acid hydroxypropyl acrylate copolymer is purchased from the strong Yilong Industry Co., Ltd. in Luoyang.
In embodiment and comparative example, the assay method of solid content is as follows:
Weigh about about 1.0g water treatment agent product sample, be accurate to 0.0002g, be placed in weighed flat
In tared dish, careful shake makes medicament natural flow, in forming one layer of uniform thin film at the bottom of ware, then puts
Enter in electrically heated drying cabinet, begin to warm up from room temperature, after being dried 4h at 120 DEG C, claim every half an hour
Amount is once until constant weight.Take out after constant weight, put into and exsiccator is cooled to room temperature, weigh.
Solid content computing formula is: solid content=[(m2-m1)/m] × 100%, wherein,
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 3.6g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 10g, acrylic acid methyl ester. 6g, acrylic acid 48g
With 25ml water, shake up；Ammonium persulfate. 4.8g and 80ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start to drip the liquid in two constant pressure funnels
Body, continuation liter high-temperature is to 85 DEG C simultaneously, controls rate of addition and makes the liquid in two constant pressure funnels
It was 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 30.1%.
Embodiment 2
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Ammonium persulfate. 4.8g and 80ml water, start stirring, makes sodium pyrosulfite fully dissolve.A constant voltage
In Dropping funnel add dimethyl diallyl ammonium chloride 10g, acrylic acid methyl ester. 6g, acrylic acid 48g and
25ml water, shakes up；Sodium pyrosulfite 3.6g and 50ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start to drip the liquid in two constant pressure funnels
Body, continuation liter high-temperature is to 85 DEG C simultaneously, controls rate of addition and makes the liquid in two constant pressure funnels
It was 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 29.5%.
Embodiment 3
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 3.6g, dimethyl diallyl ammonium chloride 10g, acrylic acid methyl ester. 6g, acrylic acid 48g
With 80ml water, start stirring, make sodium pyrosulfite fully dissolve.Add with in constant pressure funnel
Ammonium persulfate. 4.8g and 80ml water, shake up；Start to warm up, when temperature is increased to 50 DEG C, start to drip
Adding the liquid in two constant pressure funnels, continuation liter high-temperature is to 85 DEG C simultaneously, controls rate of addition and makes
Liquid in two constant pressure funnels was added dropwise to complete in 1 hour, continued insulation reaction 2 hours afterwards,
Stopping test, cool down to obtain product, the solid content of product is 31.2%.
Embodiment 4
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Isopropanol 6g and 50ml water, start stirring, makes isopropanol fully dissolve.At a constant pressure funnel
Middle addition dimethyl diallyl ammonium chloride 20g, Hydroxypropyl acrylate 6g, maleic anhydride 42g and 25ml
Water, shakes up；In another constant pressure funnel, add Ammonium persulfate. 2.4g and 80ml water, shake up；
Start to warm up, when temperature is increased to 60 DEG C, start to drip the liquid in two constant pressure funnels, with
Shi Jixu liter high-temperature, to 80 DEG C, controls rate of addition and the liquid in two constant pressure funnels is existed
It is added dropwise to complete in 0.5 hour, continues insulation reaction 3 hours afterwards, stop test, cool down to obtain product,
The solid content of product is 29.9%.
Embodiment 5
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 2.4g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 20g, acrylic acid methyl ester. 9g, itaconic acid 39g
With 30ml water, shake up；Ammonium persulfate. 7.2g and 70ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start to drip the liquid in two constant pressure funnels
Body, continuation liter high-temperature is to 80 DEG C simultaneously, controls rate of addition and makes the liquid in two constant pressure funnels
Body was added dropwise to complete in 1.5 hours, continued insulation reaction 3 hours afterwards, stopped test, cooled down to produce
Product, the solid content of product is 30.2%.
Embodiment 6
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 1.2g and 40ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 20g, Hydroxypropyl acrylate 18g, methyl-prop
Olefin(e) acid 30g and 30ml water shake up；Ammonium persulfate. 1.2g and 70ml is added in another constant pressure funnel
Water, shakes up；Start to warm up, when temperature is increased to 60 DEG C, start to drip in two constant pressure funnels
Liquid, simultaneously continue rise high-temperature to 85 DEG C, control rate of addition make in two constant pressure funnels
Liquid be added dropwise to complete in 1.5 hours, continue insulation reaction 4 hours afterwards, stop test, cooling
Obtaining product, the solid content of product is 29.7%.
Embodiment 7
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 1.2g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 30g, Hydroxypropyl acrylate 18g, maleic acid
Acid anhydride 24g and 30ml water, shake up；Ammonium persulfate. 6g and 70ml is added in another constant pressure funnel
Water, shakes up；Start to warm up, when temperature is increased to 60 DEG C, start to drip in two constant pressure funnels
Liquid, simultaneously continue rise high-temperature to 90 DEG C, control rate of addition make in two constant pressure funnels
Liquid be added dropwise to complete in 1.5 hours, continue insulation reaction 2 hours afterwards, stop test, cooling
Obtaining product, the solid content of product is 30.1%.
Embodiment 8
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Isopropanol 6g and 50ml water, start stirring.Dimethyl two allyl is added in a constant pressure funnel
Ammonium chloride 30g, ethyl acrylate 12g, acrylic acid 30g and 20ml water shake up；In another constant voltage
Dropping funnel adds Ammonium persulfate. 3.6g and 80ml water, shakes up；Start to warm up, when temperature is increased to
When 70 DEG C, starting to drip the liquid in two constant pressure funnels, continuation liter high-temperature is to 90 DEG C simultaneously,
Controlling rate of addition makes the liquid in two constant pressure funnels be added dropwise to complete in 1.5 hours, afterwards
Continuing insulation reaction 2 hours, stop test, cool down to obtain product, the solid content of product is 30.1%.
Embodiment 9
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 7.2g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 30g, Hydroxypropyl acrylate 18g, maleic acid
Acid anhydride 24g and 30ml water, shake up；Ammonium persulfate. 7.2g and 70ml is added in another constant pressure funnel
Water, shakes up；Start to warm up, when temperature is increased to 50 DEG C, start to drip in two constant pressure funnels
Liquid, simultaneously continue rise high-temperature to 75 DEG C, control rate of addition make in two constant pressure funnels
Liquid be added dropwise to complete in 1.5 hours, continue insulation reaction 2 hours afterwards, stop test, cooling
Obtaining product, the solid content of product is 30.2%.
Embodiment 10
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 7.2g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 15g, Hydroxypropyl acrylate 9g, itaconic acid 42g
With 25ml water, shake up；Ammonium persulfate. 1.2g and 75ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start to drip the liquid in two constant pressure funnels
Body, continuation liter high-temperature is to 95 DEG C simultaneously, controls rate of addition and makes the liquid in two constant pressure funnels
Body was added dropwise to complete in 1.5 hours, continued insulation reaction 3 hours afterwards, stopped test, cooled down to produce
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 pyrosulfite 2.4g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 20g, Hydroxypropyl acrylate 12g, maleic acid
Acid anhydride 30g and 30ml water, shake up addition Ammonium persulfate. 3.6g and 70ml in another constant pressure funnel
Water, shakes up；Start to warm up, when temperature is increased to 50 DEG C, start to drip in two constant pressure funnels
Liquid, simultaneously continue rise high-temperature to 95 DEG C, control rate of addition make in two constant pressure funnels
Liquid be added dropwise to complete in 1.5 hours, continue insulation reaction 3 hours afterwards, stop test, cooling
Obtaining product, the solid content of product is 30.3%.
Embodiment 12
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 4.8g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 20g, Hydroxypropyl acrylate 9g, itaconic acid 39g
With 30ml water, shake up；Ammonium persulfate. 2.4g and 70ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start to drip the liquid in two constant pressure funnels
Body, continuation liter high-temperature is to 90 DEG C simultaneously, controls rate of addition and makes the liquid in two constant pressure funnels
Body was added dropwise to complete in 1.5 hours, continued insulation reaction 3 hours afterwards, stopped test, cooled down to produce
Product, the solid content of product is 29.7%.
Embodiment 13
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 4.8g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel in add dimethyl diallyl ammonium chloride 15g, Hydroxypropyl acrylate 9g,
Itaconic acid 42g and 25ml water, shake up；Ammonium persulfate. 4.8 is added in another constant pressure funnel
G and 75ml water, shakes up；Start to warm up, when temperature is increased to 50 DEG C, start to drip two constant voltages
Liquid in Dropping funnel, continuation liter high-temperature is to 95 DEG C simultaneously, controls rate of addition and makes two constant voltages
Liquid in Dropping funnel was added dropwise to complete in 1.5 hours, continued insulation reaction 3 hours afterwards, stopped
Test, cools down to obtain product, and the solid content of product is 30.4%.
Embodiment 14
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 4.8g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 30g, Hydroxypropyl acrylate 18g, maleic acid
Acid anhydride 24g and 30ml water, shake up；Ammonium persulfate. 4.8g and 70ml is added in another constant pressure funnel
Water, shakes up；Start to warm up, when temperature is increased to 60 DEG C, start to drip in two constant pressure funnels
Liquid, simultaneously continue rise high-temperature to 90 DEG C, control rate of addition make in two constant pressure funnels
Liquid be added dropwise to complete in 1.5 hours, continue insulation reaction 2 hours afterwards, stop test, cooling
Obtaining product, the solid content of product is 30.1%.
Embodiment 15
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 4.8g and 50ml water, start stirring, makes sodium sulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 20g, Hydroxypropyl acrylate 9g, itaconic acid 39g
With 30ml water, shake up；Ammonium persulfate. 2.4g and 70ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 50 DEG C, start to drip the liquid in two constant pressure funnels
Body, continuation liter high-temperature is to 90 DEG C simultaneously, controls rate of addition and makes the liquid in two constant pressure funnels
Body was added dropwise to complete in 1.5 hours, continued insulation reaction 3 hours afterwards, stopped test, cooled down to produce
Product, the solid content of product is 29.7%.
Comparative example 1
The PDDA that Shandong Lu Yue Chemical Co., Ltd. produces, solid content is
30.2%.
Comparative example 2
Maleic anhydride/Hydroxypropyl acrylate copolymer that the strong Yilong Industry Co., Ltd. in Luoyang produces, solid content
It is 30.4%.
Comparative example 3
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium sulfite 4.8g and 50ml water, start stirring, makes sodium sulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 20g, Hydroxypropyl acrylate 9g, itaconic acid 39g
With 30ml water, shake up；Ammonium persulfate. 2.4g and 70ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 30 DEG C, start to drip the liquid in two constant pressure funnels
Body, controls rate of addition and the liquid in two constant pressure funnels was added dropwise to complete in 1.5 hours,
Continuing steady temperature afterwards to react 3 hours, stop test, cool down to obtain product, the solid content of product is
30.1%.
Comparative example 4
Add in the four-hole boiling flask equipped with agitator, reflux condenser, constant pressure funnel and thermometer
Sodium pyrosulfite 4.8g and 50ml water, start stirring, makes sodium pyrosulfite fully dissolve.A perseverance
Pressure Dropping funnel adds dimethyl diallyl ammonium chloride 20g, Hydroxypropyl acrylate 9g, itaconic acid 39g
With 30ml water, shake up；Ammonium persulfate. 2.4g and 70ml water is added in another constant pressure funnel,
Shake up；Start to warm up, when temperature is increased to 30 DEG C, start to drip the liquid in two constant pressure funnels
Body, controls rate of addition and the liquid in two constant pressure funnels was added dropwise to complete in 1.5 hours,
Continuing steady temperature afterwards to react 3 hours, stop test, cool down to obtain product, the solid content of product is
30.2%.
Comparative example 5
Water treatment agent is prepared, except for the difference that, by " Hydroxypropyl acrylate " according to the method for embodiment 12
Replacing with " 2-(Acryloyloxy)ethanol ", the solid content of the product obtained is 31.0%.
Test case 1
This test case is used for illustrating the performance of the phosphate-free water treatment agent obtained by above-described embodiment and comparative example.
Measure the pole of the phosphate-free water treatment agent of each embodiment and comparative example acquisition the most in accordance with the following methods
Limit viscosity, anticorrosion-antiscaling property and flocculating property, result is as shown in table 2, and in table 2, "/" represents not
It is measured.
(1) mensuration of limiting viscosity
Take suitable quantity of water inorganic agent sample in culture dish, with 80g/L sodium hydroxide solution adjusting sample solution
PH value to 9.0, be then placed in baking oven toasting 4h at 120 ± 2 DEG C, take out and be placed in exsiccator
It is cooled to room temperature, i.e. makes dry sample.Weigh 0.27g and be dried sample, be accurate to 0.0002g, with burning
In Bei, after dissolving with 101g/L sodium thiocyanate solution, it is transferred in 50mL volumetric flask, with sodium rhodanate
Solution is settled to scale, shakes up, test solution to be measured.This liquid is added clean through G3 acidproof filtration funnel
In the clean Ubbelohde viscometer being dried, to filling between graticule G, H, constant temperature 10-15min, with suction
Test solution is sucked C ball more than graticule E by ear ball, though with stopwatch read test solution flow out graticule E, F time
Between, METHOD FOR CONTINUOUS DETERMINATION three times, error is less than 0.2s, takes its meansigma methods ts.Carry out sodium rhodanate molten simultaneously
The blank experiment t of liquid0s。
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
The concentration of C: test solution, g/dL
(2) mensuration of calcium carbonate scale performance is hindered
Take distilled water preparation Ca2+Concentration is 600mg/L, basicity is 600mg/L, pH value is about 9.0
Test water, add appropriate water treatment agent sample and make its valid density be 10mg/L test water,
In 80 ± 1 DEG C of waters bath with thermostatic control, stand 10h, sample analysis water remains Ca2+Concentration, do sky simultaneously
White sample, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C0) × 100%/(C1-C0), wherein,
C: actual measurement Ca2+Concentration (mg/L)
C0: the Ca of blank sample2+Concentration (mg/L)
C1: the Ca in former water2+Concentration (mg/L)
(3) mensuration of corrosion inhibition
20# quality carbon steel test piece is fixed on lacing film instrument, adds appropriate in the tap water of mix homogeneously
Water treatment agent sample so that it is valid density is 10mg/L tap water, and tap water quality is shown in Table 1, permanent
Fixed temperature 45 ± 1 DEG C, keeps rotating speed 75rpm to rotate 72 hours, the weight of test piece before and after record test,
Calculate average corrosion rate.
Average corrosion rate computing formula is: F=(C × △ W)/(A × T × ρ), wherein,
C: computational constant, when being unit with mm/a (millimeter/year), C=8.76 × 107
The corrosion weight loss (g) of △ W: test specimen
Area (the cm of A: test specimen2)
T: corrosion testing time (h)
Density (the kg/m of ρ: material for test3)
Table 1
| Ca2+ | Total alkalinity | Total hardness | Cl- | SO4 2- | pH | Electrical conductivity | Total molten solid |
| 279mg/L | 154mg/L | 340mg/L | 65mg/L | 89mg/L | 8.1 | 440μs/cm | 181mg/L |
Wherein, the assay method of water quality is 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；
Total molten solid (mg/L): reference standard GB/T 14415-2007.
(4) mensuration of flocculating property
Standard turbidity uses liquid: draw the Hydrazinium sulfate solution of 10g/L of 25.0mL and 25.0mL
The hexamethylenetetramine solution of 100g/L moves in 500mL volumetric flask, shakes up.At (25 ± 3) DEG C,
Stand 24h, then with distilled water diluting to scale, shake up.Measure the above-mentioned storing solution of 75.0mL in
In 1000mL volumetric flask, it is diluted to scale, shakes up.The turbidity of this suspension is 30mg/L.
The aqueous solution that concentration is 5.0g/L it is configured in water treatment agent sample 24h before the test.
Floc test: add 1000ml standard turbidity in the beaker of 1L and use liquid, be placed on agitator
Below stirring paddle, stirring paddle is made to deviate beaker center, but from walls of beaker about 6mm；Start agitator,
Add 2mL water treatment agent sample solution after quickly stirring 10min under rotating speed 120r/min, continue fast
Speed stirring 1min；Reduce rotating speed and stop stirring, standing sedimentation after 50r/min low rate mixing 20min
After 20min, take the supernatant and analyze turbidity.
Water turbidity (mg/L) assay method reference standard GB/T 12151-1989, the turbidity value recorded
The least, illustrate that the flocculating property of water treatment agent is the best.
(5) mensuration of zinc salt scale inhibition performance
Take distilled water preparation Ca2+Concentration is 250mg/L, basicity is 250mg/L, Zn2+Concentration be 5mg/L,
PH value, in the test water of about 9.0, adds appropriate water treatment agent sample and makes its valid density be
10mg/L test water, stands 10h in 80 ± 1 DEG C of waters bath with thermostatic control, remains Zn in sample analysis water2+
Concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C0) × 100%/(C1-C0), wherein,
C: actual measurement Zn2+Concentration (mg/L)
C0: the Zn of blank sample2+Concentration (mg/L)
C1: the Zn in former water2+Concentration (mg/L)
Table 2
Data from table 2 are it can be seen that the phosphate-free water treatment agent of the present invention is applied to circulating water treatment tool
Having preferable scale-inhibiting properties and flocculating effect, corrosion of carbon steel has certain remission effect simultaneously, is a kind of
The water treatment agent of excellent performance.Owing to having preferable flocculating effect, the phosphate-free water treatment agent of the present invention is outstanding
It is applicable to the recirculated water system that turbidity is higher.
Comparing embodiment 12 with comparative example 3-5 it can be seen that according to the mode described in the inventive method
Control temperature and select the concrete kind of acrylate could obtain the phosphate-free water treatment agent of excellent performance.Ratio
Compared with embodiment 12 and embodiment 15 it can be seen that use currently preferred molecular weight regulator to obtain
Obtain the phosphate-free water treatment agent that performance is more excellent.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept 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 the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
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 should be considered as content disclosed in this invention equally.
Claims (10)
1. a phosphate-free water treatment agent, this phosphate-free water treatment agent by dimethyl diallyl ammonium chloride, no
Saturated carboxylic acid and acrylic ester polymerization obtain and the limiting viscosity of described phosphate-free water treatment agent is
0.05-0.16dL/g, preferably 0.065-0.085dL/g, wherein, described unsaturated carboxylic acid selected from acrylic acid,
Maleic acid, methacrylic acid or methylene-succinic acid, described acrylate is selected from acrylic acid methyl ester., propylene
Acetoacetic ester or Hydroxypropyl acrylate.
Phosphate-free water treatment agent the most according to claim 1, wherein, dimethyl diallyl chlorination
Ammonium, unsaturated carboxylic acid are 1:1-10:0.1-4.5, preferably 1:1.5-8:0.5-3 with the weight ratio of acrylate.
3. the method preparing phosphate-free water treatment agent, the method includes: at 50-95 DEG C, by monomer,
Initiator and molecular weight regulator mix, then continue reaction 1-4h, described monomer at 75-95 DEG C
For dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and acrylate, wherein, described unsaturated carboxylic acid
Selected from acrylic acid, maleic acid, methacrylic acid or methylene-succinic acid, described acrylate is selected from propylene
Acid methyl ester, ethyl acrylate or Hydroxypropyl acrylate；The mode of described mixing is:
A the solution of monomer and the solution of initiator are dropped in the solution of molecular weight regulator by () respectively,
Or
B the solution of monomer and the solution of molecular weight regulator are dropped in the solution of initiator by () respectively,
Or
C the solution of initiator is dropped in the mixed solution of molecular weight regulator and monomer by ().
Method the most according to claim 3, wherein, dimethyl diallyl ammonium chloride, insatiable hunger
It is 1:1-10:0.1-4.5, preferably 1:1.5-8:0.5-3 with the weight ratio of carboxylic acid Yu acrylate.
5. according to the method described in claim 3 or 4, wherein, the consumption of described initiator is monomer
The 2-12% of total consumption, described initiator is preferably in Ammonium persulfate., potassium peroxydisulfate and sodium peroxydisulfate extremely
Few one.
6. according to the method described in claim 3 or 4, wherein, the consumption of described molecular weight regulator
For the 2-12% of the total consumption of monomer, described molecular weight regulator is preferably sodium pyrosulfite or isopropanol.
Method the most according to claim 3, wherein, in mode (a), dripping of the solution of monomer
Acceleration is 25-200mL/h, and the rate of addition of the solution of initiator is 30-160mL/h；Or
In mode (b), the rate of addition of the solution of monomer is 25-200mL/h, molecular weight regulator
The rate of addition of solution is 20-120mL/h；Or
In mode (c), the rate of addition of the solution of initiator is 30-160mL/h.
8. the phosphate-free water treatment agent prepared by the method described in any one in claim 3-7.
9. the application in processing cycle water of the phosphate-free water treatment agent described in claim 1,2 or 8.
The phosphate-free water treatment agent the most according to claim 9 application in processing cycle water, wherein,
The addition of described phosphate-free water treatment agent is 10-100mg/L recirculated water, and preferably 20-60mg/L circulates
Water.
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