CN110201427A

CN110201427A - A kind of polymer defoaming agent and preparation method thereof

Info

Publication number: CN110201427A
Application number: CN201910382821.9A
Authority: CN
Inventors: 刘杨; 陈玉娟; 曹添; 黄伟; 安东尼·K·达西
Original assignee: Jiangsu Sixin Scientific-Technological Application Research Institute Co Ltd
Current assignee: Jiangsu Sixin Scientific-Technological Application Research Institute Co Ltd
Priority date: 2019-05-09
Filing date: 2019-05-09
Publication date: 2019-09-06
Also published as: WO2020224043A1

Abstract

The invention belongs to technical field of fine chemical preparations, in particular to a kind of polymer defoaming agent and preparation method thereof, the polymer defoaming agent includes acrylate polymer, organic solvent carriers, inorganic filler, catalyst；The acrylate polymer is made of following raw material components: monomer -1, monomer -2, monomer -3, alkene, diluent, initiator, chain-transferring agent；The monomer -1 is alkyl acrylate；The monomer -2 is alkyl methacrylate；The monomer -3 is acrylic acid hydroxy alkyl ester；For defoaming agent of the present invention with acrylate polymer for main active matter, which has excellent antifoaming performance, the application being particularly suitable in alkali system paper-making pulping.

Description

A kind of polymer defoaming agent and preparation method thereof

Technical field

The invention belongs to technical field of fine chemical preparations, are related to a kind of fine chemistry preparation, are a kind of more precisely Polymer defoaming agent comprising modified polyacrylate, and preparation method thereof and the application in alkali system paper-making pulping.

Background technique

In various industrial processes, the generation of foam can reduce productivity, increase defect rate, reduce product and load Rate.Contain a large amount of lignin sodium salt and other resin components in the waste water (black liquor) especially generated during paper-making pulping, Cause to separate in paper pulp, generate a large amount of foam in washing process, this certainly will will lead to detersive efficiency and process operability It is greatly reduced, leads to the decline of paper strength, foam residual mark on paper reduces that quality of finished paper etc. is various to ask Topic.Therefore, during paper-making pulping, defoaming agent is essential.

The known defoaming agent for paper-making pulping is divided into non-silicon defoaming agent and organic silicon defoamer two major classes.Common is non- Silicon defoaming agent is using mineral oil, polyethers, amide or fatty alcohol as active matter, a large amount of in use, active matter amide can be gradually Aggregation, condensation, the residual mark on paper；And mineral oil can generate tetrachloro dibenzo-p- two under prolonged high-temperature condition English (TCDD) harmful substance is disliked, personal safety and Environmental security are endangered.Organic silicon defoamer is with polysiloxanes, filler etc. for work Property object, prolonged use will lead to the reunion of hydrophobic particles, after be attached on paper, form silicon spot, cause under paper quality Drop.

Patent CN101991975B provides a kind of mineral oil antifoam agent, by mineral oil, fatty acid metal soap, fatty acid acyl Amine, white carbon black, antifoam additives and emulsifier composition, there is the foam inhibition effect that preferably disappears during papermaking, water process etc..But mine This kind of hydrocarbon ils substance of object oil can generate tetrachloro dibenzo-p- dioxin (TCDD) harmful substance when encountering high temperature, to environment and people Body health damages, and inhibits the ability shortcoming of foam in the system rich in anionic surfactant.

Patent WO9420680A1 describes a kind of defoaming agent being made of polyethers, amide for main active matter, is mainly used for Paper industry.Solves mineral oil bring environmental issue during use.But in use, since amide has Stronger hydrophobicity and be easier to deposit, spot is formed on paper, to influence production efficiency and product quality.

The organosilicon emulsion defoaming agents that patent CN102002242B is introduced are by constituent polyorganosiloxane composition, poly alkyl alcohol Ether, emulsifier, Siloxane-Oxyalkylene Copolymers and water composition, are suitable for the industries such as papermaking, weaving.Defoaming agent in the patent uses Silicone grease is as defoaming activity substance, and due to the hydrophobicity of silicone grease, silicone grease can be gradually precipitated in defoaming agent use process, is defoaming In the case that agent is accumulated for a long time, silicone grease also can largely be precipitated therewith, on the one hand will affect product quality, on the other hand can deposit It is difficult to clean in equipment or even equipment is caused to block.Therefore, although silicone grease, which is generally considered to have, defoams quick and foam inhibition Lasting characteristic, but avoid in many industrial productions using the anti-foam product containing silicone grease.

In conclusion the demand to the defoaming agent of not hydrocarbonaceous oil, EBS or silicone grease is more and more.Patent A kind of defoaming agent that CN101638871B is introduced is made of fatty acid methyl ester derivant, polyethers, natural oil, and it is wet to be suitable for papermaking The elimination of portion's process, pulping wastewater treatment and some other water phase foam.Injury of the mineral oil to environment is avoided in patent, but It is the suppression that disappears with non-silicon defoaming agent that polyethers or fatty alcohol are main active matter in the system rich in anionic surfactant It is not fully up to expectations to steep performance, the ability of foam is inhibited not to be able to satisfy industrial production demand still.So researchers are on the one hand It is improved on the basis of the defoaming agent of existing type to mitigate the above problem, on the one hand develops novel defoaming agent fundamentally It solves the above problems, esters of acrylic acid defoaming agent is a research hotspot.

What patent US5152925A was introduced is the defoaming agent using a kind of acrylic resin as main defoaming activity substance, Middle acrylate polymer is mainly with the acrylic monomers containing hydroxyl in organic diluent diisooctyl phthalate (DIDP) acrylic resin prepared in is applied to thick plasm scouring and other papermaking process as main active substances.Patent It is equally mentioned in CN102428142B and prepares defoaming agent using acrylate polymer as main active substances, wherein acrylate Polymer is by monomers such as Isooctyl acrylate monomer, acrylic acid hydroxy alkyl ester and acrylic acid in organic diluent diisooctyl adipate (DIOA) in preparation, using the acrylate polymer of preparation as the main active of defoaming agent, and with white carbon black, alkyl silicon The antifoam additives such as oil compounding, is applied to petroleum industry, water process, pigment and coating, food and beverage processing, mining industry, weaving The industries such as industry, agricultural and papermaking.The appearance of such defoaming agent can solve environmental injury problem and residue problem is precipitated in silicon, still The defoaming agent antifoaming performance of technology preparation at present still has greatly improved space.Therefore, acrylate polymer defoaming is improved The antifoaming performance of agent will be significant.

Summary of the invention

The present invention solves the above-mentioned technical problems in the prior art, and it is main for providing one kind with acrylate polymer The defoaming agent of active matter, the defoaming agent have excellent antifoaming performance, are particularly suitable in the paper-making pulping of alkali system Using.

To solve the above problems, technical scheme is as follows:

A kind of polymer defoaming agent, including acrylate polymer, organic solvent carriers, inorganic filler, catalyst；It is described The dosage of acrylate polymer account for the 10~50% of defoaming agent gross mass, the dosage of the organic solvent carriers accounts for defoaming The 40~80% of agent gross mass, the dosage of the inorganic filler account for the 0.1~15% of defoaming agent gross mass, the catalyst Dosage account for the 0.1-5% of defoaming agent gross mass.

Preferably, the dosage of the acrylate polymer accounts for the 20~40% of defoaming agent gross mass, and described is organic The dosage of solvent carrier accounts for the 50~70% of defoaming agent gross mass, and the dosage of the inorganic filler accounts for defoaming agent gross mass 0.5~10%, the dosage of the catalyst accounts for the 0.5~2% of defoaming agent gross mass.

Acrylate polymer

Preferably, the molecular weight of the acrylate polymer is between 15000~30000.

Preferably, the acrylate polymer is made of following raw material components: monomer -1, monomer -2, monomer - 3, alkene, diluent, initiator, chain-transferring agent；The monomer -1 is alkyl acrylate；The monomer -2 is methyl-prop Olefin(e) acid Arrcostab；The monomer -3 is acrylic acid hydroxy alkyl ester.

Preferably, it is total to account for acrylate polymer raw material components for total dosage of the monomer -1, monomer -2 and monomer -3 The 30~70% of quality, the dosage of the alkene account for the 0.5~5% of polymer raw material component gross mass, the diluent Dosage account for the 25~65% of polymer raw material component gross mass, the dosage of the initiator accounts for the total matter of polymer raw material component The 0.2~1% of amount, the dosage of the chain-transferring agent accounts for the 0.1~1% of polymer raw material component gross mass.

Preferably, the monomer -1, monomer -2, monomer -3 total dosage account for the total matter of acrylate polymer raw material components The 40~60% of amount, the dosage of the alkene accounts for the 1~4% of polymer raw material component gross mass；The use of the diluent Amount accounts for the 35~55% of polymer raw material component gross mass；The dosage of the initiator accounts for polymer raw material component gross mass 0.4~0.8%.The dosage of the chain-transferring agent accounts for the 0.2~0.6% of polymer raw material component gross mass.

A, monomer

Preferably, the monomer -1 accounts for the 60~80% of monomer gross mass, and monomer -2 accounts for the 5~15% of monomer gross mass, Monomer -3 accounts for the 10~30% of monomer gross mass.

Preferably, wherein monomer -1 accounts for the 65~75% of monomer gross mass, and monomer -2 accounts for the 8~12% of monomer gross mass, Monomer -3 accounts for the 15~25% of monomer gross mass.

Preferably, the monomer -1 is selected from methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, third Olefin(e) acid octadecyl ester, Isooctyl acrylate monomer.

Preferably, the monomer -2 is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, first Base dodecyl acrylate, octadecyl methacrylate, isooctyl methacrylate.

Preferably, the monomer -3 is the acrylic acid hydroxy alkyl ester as shown in following general formula:

Wherein R is the linear or branched alkyl group of 1-20 carbon atom and any position at least contains one on alkyl chain Hydroxyl；

Preferably, R is selected from 1- hydroxyethyl, 2- ethoxy, 1- hydroxypropyl, 2- hydroxypropyl, 3- hydroxypropyl, 1- hydroxyl isopropyl Base, 2- hydroxyisopropyl, 3- hydroxyisopropyl, 1- hydroxyl butyl, 2- hydroxyl butyl, 3- hydroxyl butyl or 4- hydroxyl butyl.

Preferably, the monomer -1 is Isooctyl acrylate monomer；The monomer -2 is lauryl methacrylate；It is described Monomer -3 be hydroxy-ethyl acrylate.

B, alkene

Preferably, the alkene is as shown in following general formula:

CH₂=CHR¹

Wherein R¹For the linear or branched alkyl group of 4~20 carbon atoms.

Preferably, R¹For the direct-connected alkyl of 10~16 carbon atoms.

C, diluent

Preferably, the example for suitable diluent of the invention can be selected from, but be not limited to two isodecyl of phthalic acid Ester, diisooctyl adipate, diisooctyl phthalate, dioctyl adipate, 2- ethyl -1- hexanol, isooctanol, molecular weight It is 300~2000 for 300~2000 polyethylene glycol (PEG), the polypropylene glycol (PPG) that molecular weight is 300~2000, molecular weight Polytetramethylene glycol, molecular weight be 300-2000 aliphatic alcohol polyether, can be used alone or be used in mixed way.

Preferably, the diluent is polypropylene glycol that molecular weight is 300~2000 and/or molecular weight is 300-2000 Aliphatic alcohol polyether.

D, initiator

Preferably, the initiator example for generation free radical of the invention is selected from, but is not limited to 2, the bis- (2- of 2 '-azos Methyl propionitrile), 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2- methylbutyronitriles), benzoyl peroxide；Or Redox initiator systems, such as bromate/sulfide or persulfate/ferrous iron system also can be used in person.

Preferably, the initiator is benzoyl peroxide.

E, chain-transferring agent

Preferably, the chain-transferring agent for present invention control polymer molecular weight

For lauryl mercaptan.

Organic solvent carriers

Preferably, the example for suitable organic solvent carriers of the invention can be selected from, but be not limited to phthalic acid Diisodecyl ester, diisooctyl adipate, diisooctyl phthalate, adipic acid dibutyl ester, 2- ethyl -1- hexanol, isooctanol, The poly- second that polybutene that polytetramethylene glycol that molecular weight is 300~2000, molecular weight are 400~2000, molecular weight are 300~2000 Glycol or its polyether ester formed with fatty acid, the polypropylene glycol that molecular weight is 300~2000 or its formed with fatty acid it is poly- Ether-ether, molecular weight are the aliphatic alcohol polyether of 300-2000, can be used alone or are used in mixed way.

Preferably, the organic solvent carriers are polypropylene glycol that molecular weight is 300~2000 and/or molecular weight is The aliphatic alcohol polyether of 300-2000.

Inorganic filler

Preferably, it is 150~500m that the inorganic filler, which is specific surface area,²The hydrophilic fume colloidal silica of/g.

Catalyst

Preferably, the catalyst is made of sodium hydroxide or potassium hydroxide with methyl-silicone oil agitating and heating.

Preferably, the condition of the agitating and heating are as follows: heating temperature is 50~80 DEG C, and mixing time is 0.5~3h.

Preferably, the dosage of the sodium hydroxide or potassium hydroxide is the 5% of catalyst gross mass, the dosage of methyl-silicone oil It is the 95% of catalyst gross mass.

Preferably, the methyl-silicone oil viscosity is 10~1000mPa.s.

Preferably, the catalyst is that the methyl-silicone oil for being 50~500mPa.s by potassium hydroxide and viscosity is warming up to 60 DEG C, and continue stirring 1h and be prepared.

A kind of preparation method of acrylate polymer, comprising the following steps:

(1) by 5/8 mixing of monomer -1, monomer -2, monomer -3 and the total dosage of initiator, stirring evenly keeps initiator complete Fully dissolved forms mixture a；

(2) by 1/8 mixing of alkene and the total dosage of initiator, stirring evenly is completely dissolved initiator, forms mixing Object b；

(3) diluent is added in reaction kettle, stirring is warming up to 80 DEG C, and 1/8 and chain of the total dosage of initiator is added Transfer agent stirs evenly, until initiator is completely dissolved, and releases free radical, forms mixture c；

(4) 90~100 DEG C are warming up to, the 1/3 of mixture a gross mass is added dropwise into mixture c, controls time for adding 1 ~2h forms mixture d；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90~100 DEG C, the 1/3 of mixture b gross mass is added dropwise into mixture d, control is added dropwise Time in 1~2h, forms Mischung；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90~100 DEG C it is constant, continue into Mischung be added dropwise mixture a gross mass 1/3, control drop In 1~2h between added-time, mixture f is formed；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b gross mass into mixture f, control at 90~100 DEG C Time for adding forms mixture g in 1~2h；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90~100 DEG C it is constant, continue that remaining mixture a is added dropwise into mixture g, control be added dropwise Time in 1~2h, forms mixture h；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90~100 DEG C, remaining mixture b is added dropwise into mixture h, control time for adding In 1~2h, mixture i is formed；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continue to keep the temperature 1~2h at 90~100 DEG C, then be continuously added into kettle remaining Initiator, and continue to keep the temperature 2~3h at 90~100 DEG C, form mixture j；

(11) after wait keep the temperature, 0.5~3h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed Small molecular weight impurity is removed, acrylate polymer is obtained.

Small molecular weight impurity of the present invention refers to the monomer -1 of unreacted monomer, monomer -2, monomer -3 and other small point Sub- raw material components.

Acrylate copolymer and inorganic filler are carried out hydroxyl by a kind of preparation method of polymer defoaming agent under alkaline condition Base, which is condensed, is made polymer defoaming agent.

The preparation method comprises the following steps:

Step 1, acrylate copolymer and inorganic filler are added in reaction kettle, stir evenly and is warming up to 50~80 DEG C, catalyst is then added, and be warming up to 90~100 DEG C, reacts 1-2h；Then it is down to room temperature, forms intermediate；

Step 2, continue that organic solvent carriers are added into reaction kettle, and open and be uniformly mixed to get institute of the present invention The polymer defoaming agent stated.

Polymer defoaming agent of the present invention is to defoam in alkali system paper-making pulping system, apply in foam inhibition.

Compared with the existing technology, advantages of the present invention is as follows,

For defoaming agent of the present invention with acrylate polymer for main active matter, which has the excellent antifoaming ability that disappear Can, the application being particularly suitable in alkali system paper-making pulping；Acrylate polymer is with alkyl acrylate, methyl-prop Olefin(e) acid Arrcostab, acrylic acid hydroxy alkyl ester are that monomer is changed by specific process polymerisation by special Long carbon chain monomer Property, while the molecular weight for controlling polymer effectively raises the later period foam inhibition ability of polymer between 15000~30000； Then hydroxyl condensation is carried out under alkaline condition with hydrophilic white carbon black, modification again is carried out to polymer, it is significantly more efficient to mention The high defoaming capacity of polymer.

Specific embodiment

In the examples below, the example of acrylate polymer k is as follows:

In the examples below, the example of alkene B is as follows:

In the examples below, the example of diluent C is as follows

Acrylate copolymer embodiment and comparative example are as follows:

Embodiment 1-1

(1) by 26g Isooctyl acrylate monomer, 4.8g lauryl methacrylate, 9.2g hydroxy-ethyl acrylate and 0.5g mistake Benzoyl Oxide mixing, stirring evenly is completely dissolved initiator, forms mixture a1；

(2) 3.6g alkene B1 and 0.1g benzoyl peroxide is mixed, stirring evenly is completely dissolved initiator, shape Resulting mixture b1；

(3) by 55g diluent C1 be added reaction kettle in, stirring be warming up to 80 DEG C, and be added 0.1g benzoyl peroxide with And 0.6g chain-transferring agent lauryl mercaptan stirs evenly, until benzoyl peroxide is completely dissolved, and releases free radical, is formed Mixture c1；

(4) 90 DEG C are warming up to, the 1/3 of mixture a1 gross mass is added dropwise into mixture c1, controls time for adding in 1h, shape Resulting mixture d1；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b1 gross mass, when control is added dropwise is added dropwise into mixture d1 Between in 1h, form Mischung 1；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 1 be added dropwise mixture a1 gross mass 1/3, control drop In 1h between added-time, mixture f1 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b1 gross mass into mixture f1, control drop at 90 DEG C In 1h between added-time, mixture g1 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a1 is added dropwise into mixture g1, control time for adding In 1h, mixture h1 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b1 is added dropwise into mixture h1, control time for adding exists 1h forms mixture i1；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, and the mistake of remaining 0.1g is then continuously added into kettle Benzoyl Oxide, and continue to keep the temperature 2h at 90 DEG C, form mixture j1；

(11) after wait keep the temperature, 0.5h is distilled at vacuum degree -0.09MPa, 90 DEG C of temperature, removes small molecular weight impurity, Obtain acrylate polymer K1.

Embodiment 1-2

(1) by 45g Isooctyl acrylate monomer, 6g lauryl methacrylate, 9g hydroxy-ethyl acrylate and 0.25g2,2 '- Azo bis- (2- methylbutyronitriles) mixing, stirring evenly is completely dissolved initiator, forms mixture a2；

(2) by 1g alkene B2 and 0.05g2,2 '-azos bis- (2- methylbutyronitriles) mixing, stirring evenly keeps initiator complete Fully dissolved forms mixture b2；

(3) 38.4g diluent C2 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.05g2 is added, and 2 '-azos are double (2- methylbutyronitrile) and 0.2g chain-transferring agent lauryl mercaptan stir evenly, until 2,2 '-azos bis- (2- methylbutyronitriles) are complete Fully dissolved, and free radical is released, form mixture c2；

(4) 100 DEG C are warming up to, the 1/3 of mixture a2 gross mass is added dropwise into mixture c2, control time for adding in 2h, Form mixture d2；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90~100 DEG C, the 1/3 of mixture b2 gross mass is added dropwise into mixture d2, control drop In 2h between added-time, Mischung 2 is formed；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 100 DEG C it is constant, continue into Mischung 2 be added dropwise mixture a2 gross mass 1/3, control drop In 2h between added-time, mixture f2 is formed；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b2 gross mass into mixture f2, control drop at 100 DEG C In 2h between added-time, mixture g2 is formed；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 100 DEG C it is constant, continue that remaining mixture a2 is added dropwise into mixture g2, control be added dropwise when Between in 2h, form mixture h2；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 100 DEG C, remaining mixture b2 is added dropwise into mixture h2, control time for adding exists 2h forms mixture i2；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 2h at 100 DEG C, then continuously adds remaining 0.05g's into kettle 2,2 '-azos are bis- (2- methylbutyronitrile), and continue to keep the temperature 3h at 100 DEG C, form mixture j2；

(11) after wait keep the temperature, 1h is distilled at vacuum degree -0.1MPa, 110 DEG C of temperature, is removed small molecular weight impurity, is obtained To acrylate polymer K2.

Embodiment 1-3

(1) by 42g Isooctyl acrylate monomer, 10.5g lauryl methacrylate, 17.5g hydroxy-ethyl acrylate and 0.625g2,2 '-azos bis- (2,4- methyl pentane nitriles) mixing, stirring evenly is completely dissolved initiator, forms mixture a3；

(2) by 3g alkene B3 and 0.125g2,2 '-azos bis- (2,4- methyl pentane nitriles) mixing, stirring evenly makes to draw Hair agent is completely dissolved, and forms mixture b3；

(3) 25g diluent C3 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.125g2 is added, and 2 '-azos are double (2,4- methyl pentane nitrile) and 1g chain-transferring agent lauryl mercaptan stir evenly, until crossing bis- (2, the 4- dimethyl of 2,2 '-azos Valeronitrile) it is completely dissolved, and free radical is released, form mixture c3；

(4) 95 DEG C are warming up to, the 1/3 of mixture a3 gross mass is added dropwise into mixture c3, controls time for adding in 1h, shape Resulting mixture d3；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 95 DEG C, the 1/3 of mixture b3 gross mass, when control is added dropwise is added dropwise into mixture d3 Between in 1h, form Mischung 3；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 95 DEG C it is constant, continue into Mischung 3 be added dropwise mixture a3 gross mass 1/3, control drop In 1h between added-time, mixture f3 is formed；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b3 gross mass into mixture f3, control drop at 95 DEG C In 1h between added-time, mixture g3 is formed；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 95 DEG C it is constant, continue that remaining mixture a3 is added dropwise into mixture g3, control time for adding In 1h, mixture h3 is formed；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 95 DEG C, remaining mixture b3 is added dropwise into mixture h3, control time for adding exists 1h forms mixture i3；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 95 DEG C, and remaining 0.06251g is then continuously added into kettle 2,2 '-azos it is bis- (2,4- methyl pentane nitrile), and continue to keep the temperature 3h at 95 DEG C, form mixture j3；

(11) after wait keep the temperature, 3h is distilled at vacuum degree -0.95MPa, 100 DEG C of temperature, is removed small molecular weight impurity, is obtained To acrylate polymer K3.

Embodiment 1-4

(1) by 24g Isooctyl acrylate monomer, 1.5g lauryl methacrylate, 4.5g hydroxy-ethyl acrylate and 0.125g Sodium peroxydisulfate/ferrous sulfate mixing, stirring evenly is completely dissolved initiator, forms mixture a4；

(2) 5g alkene B4 and 0.025g sodium peroxydisulfate/ferrous sulfate are mixed, stirring evenly keeps initiator completely molten Solution forms mixture b4；

(3) 64.7g diluent C4 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.025g sodium peroxydisulfate/sulphur is added Sour ferrous and 0.1g chain-transferring agent lauryl mercaptan stirs evenly, and is completely dissolved until crossing sodium peroxydisulfate/ferrous sulfate, and release Free radical is released, mixture c4 is formed；

(4) 90 DEG C are warming up to, the 1/3 of mixture a4 gross mass is added dropwise into mixture c4, controls time for adding in 2h, shape Resulting mixture d4；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b4 gross mass, when control is added dropwise is added dropwise into mixture d4 Between in 2h, form Mischung 4；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 4 be added dropwise mixture a4 gross mass 1/3, control drop In 1h between added-time, mixture f4 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b4 gross mass into mixture f4, control drop at 90 DEG C In 1h between added-time, mixture g4 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a4 is added dropwise into mixture g4, control time for adding In 1h, mixture h4 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b4 is added dropwise into mixture h4, control time for adding exists 1h forms mixture i4；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, then continuously adds remaining 0.025g's into kettle Sodium peroxydisulfate/ferrous sulfate, and continue to keep the temperature 3h at 90 DEG C, form mixture j4；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K4.

Embodiment 1-5

(1) by 25.6g Isooctyl acrylate monomer, 3.9g lauryl methacrylate, 3.3g hydroxy-ethyl acrylate and 0.5g Sodium bromate/vulcanized sodium mixing, stirring evenly is completely dissolved initiator, forms mixture a5；

(2) 0.5g alkene B5 and 0.1g sodium bromate/vulcanized sodium are mixed, stirring evenly is completely dissolved initiator, shape Resulting mixture b5；

(3) by 65g diluent C5 be added reaction kettle in, stirring be warming up to 80 DEG C, and be added 0.1g sodium bromate/vulcanized sodium with And 0.9g chain-transferring agent lauryl mercaptan stirs evenly, until perbromic acid sodium/vulcanized sodium is completely dissolved, and releases free radical, Form mixture c5；

(4) 90 DEG C are warming up to, the 1/3 of mixture a5 gross mass is added dropwise into mixture c5, controls time for adding in 2h, shape Resulting mixture d5；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b5 gross mass, when control is added dropwise is added dropwise into mixture d5 Between in 2h, form Mischung 5；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 5 be added dropwise mixture a4 gross mass 1/3, control drop In 1h between added-time, mixture f5 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b5 gross mass into mixture f5, control drop at 90 DEG C In 1h between added-time, mixture g5 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a5 is added dropwise into mixture g5, control time for adding In 1h, mixture h5 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b5 is added dropwise into mixture h5, control time for adding exists 1h forms mixture i5；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, and the bromine of remaining 0.1g is then continuously added into kettle Sour sodium/vulcanized sodium, and continue to keep the temperature 3h at 90 DEG C, form mixture j5；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K5.

Embodiment 1-6

(1) by 43.1g Isooctyl acrylate monomer, 5.6g lauryl methacrylate, 20.8g hydroxy-ethyl acrylate and 0.375g2,2 '-azos bis- (2- methyl propionitrile) mixing, stirring evenly is completely dissolved initiator, forms mixture a6；

(2) by 4.5g alkene B6 and 0.075g2,2 '-azos bis- (2- methyl propionitrile) mixing, stirring evenly makes to cause Agent is completely dissolved, and forms mixture b6；

(3) by 25g diluent C6 be added reaction kettle in, stirring be warming up to 80 DEG C, and be added 0.075g isooctanol and 0.4g chain-transferring agent lauryl mercaptan stirs evenly, and is completely dissolved until crossing 2,2 '-azos bis- (2- methyl propionitrile), and release Free radical forms mixture c6；

(4) 90 DEG C are warming up to, the 1/3 of mixture a5 gross mass is added dropwise into mixture c6, controls time for adding in 2h, shape Resulting mixture d6；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b6 gross mass, when control is added dropwise is added dropwise into mixture d6 Between in 2h, form Mischung 6；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 6 be added dropwise mixture a6 gross mass 1/3, control drop In 1h between added-time, mixture f6 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b6 gross mass into mixture f6, control drop at 90 DEG C In 1h between added-time, mixture g6 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a6 is added dropwise into mixture g6, control time for adding In 1h, mixture h6 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b6 is added dropwise into mixture h6, control time for adding exists 1h forms mixture i6；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, then continuously adds remaining 0.075g's into kettle 2,2 '-azos are bis- (2- methyl propionitrile), and continue to keep the temperature 3h at 90 DEG C, form mixture j6；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K6.

Embodiment 1-7

(1) by 38.7g methyl acrylate, 7.2g lauryl methacrylate, 13.7g hydroxy-ethyl acrylate and 0.5g mistake Benzoyl Oxide mixing, stirring evenly is completely dissolved initiator, forms mixture a7；

(2) 4g alkene B1 and 0.1g benzoyl peroxide is mixed, stirring evenly is completely dissolved initiator, is formed Mixture b7；

(3) by 35g diluent C1 be added reaction kettle in, stirring be warming up to 80 DEG C, and be added 0.1g benzoyl peroxide with And 0.6g chain-transferring agent lauryl mercaptan stirs evenly, until benzoyl peroxide is completely dissolved, and releases free radical, is formed Mixture c1；

(4) 90 DEG C are warming up to, the 1/3 of mixture a7 gross mass is added dropwise into mixture c1, controls time for adding in 1h, shape Resulting mixture d7；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b7 gross mass, when control is added dropwise is added dropwise into mixture d7 Between in 1h, form Mischung 7；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 7 be added dropwise mixture a7 gross mass 1/3, control drop In 1h between added-time, mixture f7 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b7 gross mass into mixture f7, control drop at 90 DEG C In 1h between added-time, mixture g7 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a7 is added dropwise into mixture g7, control time for adding In 1h, mixture h7 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b7 is added dropwise into mixture h7, control time for adding exists 1h forms mixture i7；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, and the mistake of remaining 0.1g is then continuously added into kettle Benzoyl Oxide, and continue to keep the temperature 2h at 90 DEG C, form mixture j7；

(11) after wait keep the temperature, 0.5h is distilled at vacuum degree -0.09MPa, 90 DEG C of temperature, removes small molecular weight impurity, Obtain acrylate polymer K7.

Embodiment 1-8

(1) by 45g octadecyl acrylate, 6g lauryl methacrylate, 9g hydroxy-ethyl acrylate and 0.25g2,2 '- Azo bis- (2- methylbutyronitriles) mixing, stirring evenly is completely dissolved initiator, forms mixture a8；

(4) 100 DEG C are warming up to, the 1/3 of mixture a8 gross mass is added dropwise into mixture c2, control time for adding in 2h, Form mixture d8；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90~100 DEG C, the 1/3 of mixture b2 gross mass is added dropwise into mixture d8, control drop In 2h between added-time, Mischung 8 is formed；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 100 DEG C it is constant, continue into Mischung 8 be added dropwise mixture a2 gross mass 1/3, control drop In 2h between added-time, mixture f8 is formed；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b2 gross mass into mixture f8, control drop at 100 DEG C In 2h between added-time, mixture g8 is formed；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 100 DEG C it is constant, continue that remaining mixture a8 is added dropwise into mixture g8, control be added dropwise when Between in 2h, form mixture h8；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 100 DEG C, remaining mixture b2 is added dropwise into mixture h8, control time for adding exists 2h forms mixture i8；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 2h at 100 DEG C, then continuously adds remaining 0.05g's into kettle 2,2 '-azos are bis- (2- methylbutyronitrile), and continue to keep the temperature 3h at 100 DEG C, form mixture j8；

(11) after wait keep the temperature, 1h is distilled at vacuum degree -0.1MPa, 110 DEG C of temperature, is removed small molecular weight impurity, is obtained To acrylate polymer K8.

Embodiment 1-9

(1) by 25.6g dodecyl acrylate, 3.9g lauryl methacrylate, 3.3g hydroxy-ethyl acrylate and 0.5g Sodium bromate/vulcanized sodium mixing, stirring evenly is completely dissolved initiator, forms mixture a9；

(4) 90 DEG C are warming up to, the 1/3 of mixture a9 gross mass is added dropwise into mixture c5, controls time for adding in 2h, shape Resulting mixture d9；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b5 gross mass, when control is added dropwise is added dropwise into mixture d9 Between in 2h, form Mischung 9；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 9 be added dropwise mixture a9 gross mass 1/3, control drop In 1h between added-time, mixture f9 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b5 gross mass into mixture f9, control drop at 90 DEG C In 1h between added-time, mixture g9 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a9 is added dropwise into mixture g9, control time for adding In 1h, mixture h9 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b5 is added dropwise into mixture h9, control time for adding exists 1h forms mixture i9；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, and the bromine of remaining 0.1g is then continuously added into kettle Sour sodium/vulcanized sodium, and continue to keep the temperature 3h at 90 DEG C, form mixture j9；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K9.

Embodiment 1-10

(1) by 42g Isooctyl acrylate monomer, 10.5g methyl methacrylate, 17.5g hydroxy-ethyl acrylate and 0.625g2,2 '-azos bis- (2,4- methyl pentane nitriles) mixing, stirring evenly is completely dissolved initiator, forms mixture a10；

(3) 25g diluent C3 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.125g2 is added, and 2 '-azos are double (2,4- methyl pentane nitrile) and 1g chain-transferring agent lauryl mercaptan stir evenly, until 2, bis- (2, the 4- dimethyl-pentens of 2 '-azos Nitrile) it is completely dissolved, and free radical is released, form mixture c3；

(4) 95 DEG C are warming up to, the 1/3 of mixture a3 gross mass is added dropwise into mixture c3, controls time for adding in 1h, shape Resulting mixture d10；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 95 DEG C, the 1/3 of mixture b3 gross mass, when control is added dropwise is added dropwise into mixture d3 Between in 1h, form Mischung 10；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 95 DEG C it is constant, continue into Mischung 10 be added dropwise mixture a10 gross mass 1/3, control Time for adding forms mixture f10 in 1h；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b3 gross mass into mixture f10, control drop at 95 DEG C In 1h between added-time, mixture g10 is formed；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 95 DEG C it is constant, continue that remaining mixture a10 is added dropwise into mixture g10, control be added dropwise when Between in 1h, form mixture h10；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 95 DEG C, remaining mixture b3 is added dropwise into mixture h3, control time for adding exists 1h forms mixture i10；Guarantee temperature control at 95 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 95 DEG C, then continuously adds remaining 0.125g's into kettle 2,2 '-azos are bis- (2,4- methyl pentane nitrile), and continue to keep the temperature 3h at 95 DEG C, form mixture j10；

(11) after wait keep the temperature, 3h is distilled at vacuum degree -0.95MPa, 100 DEG C of temperature, is removed small molecular weight impurity, is obtained To acrylate polymer K10.

Embodiment 1-11

(1) by 24g Isooctyl acrylate monomer, 1.5g octadecyl methacrylate, 4.5g hydroxy-ethyl acrylate and 0.125g Sodium peroxydisulfate and ferrous sulfate mixing, stirring evenly is completely dissolved initiator, forms mixture a11；

(2) 5g alkene B4 and 0.025g sodium peroxydisulfate and ferrous sulfate are mixed, stirring evenly keeps initiator completely molten Solution forms mixture b4；

(3) by 64.7g diluent C4 be added reaction kettle in, stirring be warming up to 80 DEG C, and be added 0.025g sodium peroxydisulfate and Ferrous sulfate and 0.1g chain-transferring agent lauryl mercaptan stir evenly, until sodium peroxydisulfate and ferrous sulfate are completely dissolved, and Free radical is released, mixture c4 is formed；

(4) 90 DEG C are warming up to, the 1/3 of mixture a11 gross mass is added dropwise into mixture c4, control time for adding in 2h, Form mixture d11；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b4 gross mass, when control is added dropwise is added dropwise into mixture d11 Between in 2h, form Mischung 11；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 11 be added dropwise mixture a11 gross mass 1/3, control Time for adding forms mixture f11 in 1h；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b4 gross mass into mixture f11, control drop at 90 DEG C In 1h between added-time, mixture g11 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a11 is added dropwise into mixture g11, control be added dropwise when Between in 1h, form mixture h11；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b4 is added dropwise into mixture h11, control time for adding exists 1h forms mixture i11；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, then continuously adds remaining 0.025g's into kettle Sodium peroxydisulfate and ferrous sulfate, and continue to keep the temperature 3h at 90 DEG C, form mixture j11；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K11.

Embodiment 1-12

(1) by 43.1g Isooctyl acrylate monomer, 5.6g butyl methacrylate, 20.8g hydroxy-ethyl acrylate and 0.375g2,2 '-azos bis- (2- methyl propionitrile) mixing, stirring evenly is completely dissolved initiator, forms mixture a12；

(3) 25g diluent C6 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.075g2 is added, and 2 '-azos are double (2- methyl propionitrile) and 0.4g chain-transferring agent lauryl mercaptan stir evenly, until it is bis- (2- methyl propionitrile) to cross 2,2 '-azos It is completely dissolved, and releases free radical, form mixture c6；

(4) 90 DEG C are warming up to, the 1/3 of mixture a12 gross mass is added dropwise into mixture c6, control time for adding in 2h, Form mixture d12；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b6 gross mass, when control is added dropwise is added dropwise into mixture d12 Between in 2h, form Mischung 12；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 12 be added dropwise mixture a12 gross mass 1/3, control Time for adding forms mixture f12 in 1h；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b6 gross mass into mixture f12, control drop at 90 DEG C In 1h between added-time, mixture g12 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a12 is added dropwise into mixture g12, control be added dropwise when Between in 1h, form mixture h12；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b6 is added dropwise into mixture h12, control time for adding exists 1h forms mixture i12；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, then continuously adds remaining 0.075g's into kettle 2,2 '-azos are bis- (2- methyl propionitrile), and continue to keep the temperature 3h at 90 DEG C, form mixture j12；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K12.Measuring polymer molecular weight is 20000.

Embodiment 1-13

(1) by 45g Isooctyl acrylate monomer, 6g lauryl methacrylate, 9g hydroxypropyl acrylate and 0.25g2,2 '- Azo bis- (2- methylbutyronitriles) mixing, stirring evenly is completely dissolved initiator, forms mixture a13；

(4) 100 DEG C are warming up to, the 1/3 of mixture a13 gross mass is added dropwise into mixture c2, control time for adding in 2h, Form mixture d13；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90~100 DEG C, the 1/3 of mixture b2 gross mass is added dropwise into mixture d13, control Time for adding forms Mischung 13 in 2h；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 100 DEG C it is constant, continue into Mischung 13 be added dropwise mixture a13 gross mass 1/3, control Time for adding forms mixture f13 in 2h；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b2 gross mass into mixture f13, control at 100 DEG C Time for adding forms mixture g13 in 2h；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 100 DEG C it is constant, continue that remaining mixture a13 is added dropwise into mixture g13, control be added dropwise Time in 2h, forms mixture h13；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 100 DEG C, remaining mixture b2 is added dropwise into mixture h13, control time for adding exists 2h forms mixture i13；Guarantee temperature control at 100 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 2h at 100 DEG C, then continuously adds remaining 0.05g's into kettle 2,2 '-azos are bis- (2- methylbutyronitrile), and continue to keep the temperature 3h at 100 DEG C, form mixture j13；

(11) after wait keep the temperature, 1h is distilled at vacuum degree -0.1MPa, 110 DEG C of temperature, is removed small molecular weight impurity, is obtained To acrylate polymer K13.

Embodiment 1-14

(1) by 24g Isooctyl acrylate monomer, 1.5g lauryl methacrylate, 4.5g hy-droxybutyl and 0.125g Sodium peroxydisulfate and ferrous sulfate mixing, stirring evenly is completely dissolved initiator, forms mixture a14；

(4) 90 DEG C are warming up to, the 1/3 of mixture a14 gross mass is added dropwise into mixture c4, control time for adding in 2h, Form mixture d14；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b4 gross mass, when control is added dropwise is added dropwise into mixture d14 Between in 2h, form Mischung 14；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 14 be added dropwise mixture a14 gross mass 1/3, control Time for adding forms mixture f14 in 1h；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b4 gross mass into mixture f14, control drop at 90 DEG C In 1h between added-time, mixture g14 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a14 is added dropwise into mixture g14, control be added dropwise when Between in 1h, form mixture h14；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b4 is added dropwise into mixture h14, control time for adding exists 1h forms mixture i14；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, then continuously adds remaining 0.025g's into kettle Sodium peroxydisulfate and ferrous sulfate, and continue to keep the temperature 3h at 90 DEG C, form mixture j14；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K14.

Embodiment 1-15

(1) by 43.1g Isooctyl acrylate monomer, 5.6g lauryl methacrylate, 20.8g dihydroxypropyl isopropyl ester and 0.375g2,2 '-azos bis- (2- methyl propionitrile) mixing, stirring evenly is completely dissolved initiator, forms mixture a15；

(4) 90 DEG C are warming up to, the 1/3 of mixture a15 gross mass is added dropwise into mixture c6, control time for adding in 2h, Form mixture d15；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90 DEG C, the 1/3 of mixture b6 gross mass, when control is added dropwise is added dropwise into mixture d15 Between in 2h, form Mischung 15；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90 DEG C it is constant, continue into Mischung 15 be added dropwise mixture a15 gross mass 1/3, control Time for adding forms mixture f15 in 1h；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b6 gross mass into mixture f15, control drop at 90 DEG C In 1h between added-time, mixture g15 is formed；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90 DEG C it is constant, continue that remaining mixture a15 is added dropwise into mixture g15, control be added dropwise when Between in 1h, form mixture h15；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90 DEG C, remaining mixture b6 is added dropwise into mixture h15, control time for adding exists 1h forms mixture i15；Guarantee temperature control at 90 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90 DEG C, then continuously adds remaining 0.075g's into kettle 2,2 '-azos are bis- (2- methyl propionitrile), and continue to keep the temperature 3h at 90 DEG C, form mixture j15；

(11) after wait keep the temperature, 2h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K15.Measuring polymer molecular weight is 20000.

Comparative example 1-1

(1) by 26.52g Isooctyl acrylate monomer, 4.896g lauryl methacrylate, 9.3842g hydroxy-ethyl acrylate with And the mixing of 0.3125g benzoyl peroxide, stirring evenly is completely dissolved initiator, forms mixture a1；

(2) 3.5g alkene B1 and 0.0625g benzoyl peroxide is mixed, stirring evenly is completely dissolved initiator, Form mixture b1；

(3) 55g diluent C1 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.0625g benzoyl peroxide is added And 0.2g chain-transferring agent lauryl mercaptan stirs evenly, until benzoyl peroxide is completely dissolved, and releases free radical, shape Resulting mixture c1；

(4) 90~100 DEG C are warming up to, mixture a1 is added dropwise into mixture c1, control time for adding forms mixing in 3h Object d- I；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90~100 DEG C, mixture b1 is added dropwise into mixture d- I, control time for adding exists 3h forms Mischung-I；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(6) after being added dropwise to complete, continuation keeps the temperature 1h at 90~100 DEG C, then continuously adds into kettle remaining The benzoyl peroxide of 0.0625g, and continue to keep the temperature 2h at 90~100 DEG C, form mixture j- I；

(7) after wait keep the temperature, 0.5h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K- I.Measuring polymer molecular weight is 30000.

Comparative example 1-2

(1) by 39g Isooctyl acrylate monomer, 6g lauryl methacrylate, 15g hydroxy-ethyl acrylate and 0.25g peroxide Change benzoyl mixing, stirring evenly is completely dissolved initiator, forms mixture a2；

(2) 4g alkene B2 and 0.05g benzoyl peroxide is mixed, stirring evenly is completely dissolved initiator, is formed Mixture b2；

(3) 34.8g diluent C2 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.05g benzoyl peroxide is added And 0.8g chain-transferring agent lauryl mercaptan stirs evenly, until benzoyl peroxide is completely dissolved, and releases free radical, shape Resulting mixture c- II；

(4) 90~100 DEG C are warming up to, the 1/3 of mixture a2 gross mass is added dropwise into mixture c- II, controls time for adding In 2h, mixture d- II is formed；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90~100 DEG C, the 1/3 of mixture b2 gross mass is added dropwise into mixture d- II, control Time for adding forms Mischung-II in 2h；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90~100 DEG C it is constant, continue into Mischung-II be added dropwise mixture a2 gross mass 1/3, Time for adding is controlled in 2h, forms mixture f- II；During dropwise addition by recirculated water or ice bath guarantee temperature control 90~ 100℃；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b2 gross mass into Mischung-II, control at 90~100 DEG C Time for adding forms mixture g- II in 2h；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(8) maintain the temperature at 90~100 DEG C it is constant, continue that remaining mixture a2 is added dropwise into mixture g- II, control Time for adding forms mixture h- II in 2h；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90~100 DEG C, remaining mixture b2 is added dropwise into mixture h- II, control is added dropwise Time in 2h, forms mixture i- II；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 2h at 90~100 DEG C, then continuously adds into kettle remaining The benzoyl peroxide of 0.05g, and continue to keep the temperature 3h at 90~100 DEG C, form mixture j- II；

(11) after wait keep the temperature, 1h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed small Molecular impurity obtains acrylate polymer K- II.Measuring polymer molecular weight is 10000.

Comparative example 1-3

(1) by 35g Isooctyl acrylate monomer, 5g lauryl methacrylate, 10g hydroxy-ethyl acrylate and 0.5g peroxidating Benzoyl mixing, stirring evenly is completely dissolved initiator, forms mixture a3；

(2) 1g alkene B3 and 0.1g benzoyl peroxide is mixed, stirring evenly is completely dissolved initiator, is formed Mixture b3；

(3) 47.8g diluent C3 is added in reaction kettle, stirring is warming up to 80 DEG C, and 0.1g benzoyl peroxide is added It stirs evenly, until benzoyl peroxide is completely dissolved, and releases free radical, forms mixture c- III；

(4) 90~100 DEG C are warming up to, the 1/3 of mixture a3 gross mass is added dropwise into mixture c- III, controls time for adding In 1h, mixture d- III is formed；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(5) continue to maintain the temperature at 90~100 DEG C, the 1/3 of mixture b3 gross mass is added dropwise into mixture d- III, control Time for adding forms Mischung-III in 1h；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(6) maintain the temperature at 90~100 DEG C it is constant, continue into Mischung-III be added dropwise mixture a3 gross mass 1/3, Time for adding is controlled in 1h, forms mixture f- III；During dropwise addition by recirculated water or ice bath guarantee temperature control 90~ 100℃；

(7) temperature in kettle is kept to continue to be added dropwise the 1/3 of mixture b3 gross mass into Mischung-III at 90~100 DEG C, Time for adding is controlled in 1h, forms mixture g- III；During dropwise addition by recirculated water or ice bath guarantee temperature control 90~ 100℃；

(8) maintain the temperature at 90~100 DEG C it is constant, continue that remaining mixture a3 is added dropwise into mixture g- III, control Time for adding forms mixture h- III in 1h；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(9) continue to maintain the temperature at 90~100 DEG C, remaining mixture b3 is added dropwise into mixture h- III, control is added dropwise Time in 1h, forms mixture i- III；Guarantee temperature control at 90~100 DEG C by recirculated water or ice bath during dropwise addition；

(10) after being added dropwise to complete, continuation keeps the temperature 1h at 90~100 DEG C, and remaining 0.1g is then continuously added into kettle Benzoyl peroxide, and continue to keep the temperature 3h at 90~100 DEG C, form mixture j- III；

(11) after wait keep the temperature, 0.5h is distilled at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature, is removed Small molecular weight impurity obtains acrylate polymer K- III.Measuring polymer molecular weight is 40000.

The embodiment and comparative example of polymer defoaming agent is as follows:

Embodiment 2-1

1, by the 20g hydrophilic fume colloidal silica of acrylate copolymer K1 and 8g (specific surface area 150m²/ g) it is added to instead It answers in kettle, after mixing evenly, is warming up to 50 DEG C, the 2g catalyst H1 (first that 5g potassium hydroxide is 50mPa.s with 95g viscosity is added Base silicone oil is obtained in 60 DEG C of reaction 1h), 100 DEG C are warming up to, after reacting 1h, room temperature is down to, forms intermediate M1；

2, continue that 70gPPG300 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N1.

Embodiment 2-2

1, by the 40g hydrophilic fume colloidal silica of acrylate copolymer K2 and 9.5g (specific surface area 500m²/ g) it is added to In reaction kettle, after mixing evenly, 80 DEG C are warming up to, 0.5g catalyst H2 is added, and (5g potassium hydroxide is 500mPa.s with 95g viscosity Methyl-silicone oil obtained in 60 DEG C of reaction 1h), be warming up to 90 DEG C, after reacting 2h, be down to room temperature, form intermediate M2；

2, continue that 50gPPG1000 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N2.

Embodiment 2-3

1, by the 10g hydrophilic fume colloidal silica of acrylate copolymer K3 and 10g (specific surface area 200m²/ g) it is added to instead It answers in kettle, after mixing evenly, is warming up to 60 DEG C, the 5g catalyst H3 (first that 5g potassium hydroxide is 100mPa.s with 95g viscosity is added Base silicone oil is obtained in 60 DEG C of reaction 1h), 95 DEG C are warming up to, after reacting 1.5h, room temperature is down to, forms intermediate M3；

2, continue that 75gPPG2000 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N3.

Embodiment 2-4

1, by the 19.8g hydrophilic fume colloidal silica of acrylate copolymer K4 and 0.1g (specific surface area 250m²/ g) it is added Into reaction kettle, after mixing evenly, it is warming up to 70 DEG C, 0.1g catalyst H4 is added, and (5g potassium hydroxide is with 95g viscosity The methyl-silicone oil of 300mPa.s is obtained in 60 DEG C of reaction 1h), 95 DEG C are warming up to, after reacting 2h, room temperature is down to, forms intermediate M4；

2, continuing the addition 50g aliphatic alcohol polyether into reaction kettle, (fatty alcohol is initiator, molecular weight 300, EO, PO copolymerization Object), 30gPPG1000, and open be uniformly mixed to get polymer defoaming agent N4.

Embodiment 2-5

1, by the 50g hydrophilic fume colloidal silica of acrylate copolymer K5 and 12g (specific surface area 300m²/ g) it is added to instead It answers in kettle, after mixing evenly, is warming up to 50 DEG C, the 3g catalyst H5 (first that 5g potassium hydroxide is 300mPa.s with 95g viscosity is added Base silicone oil is obtained in 60 DEG C of reaction 1h), 100 DEG C are warming up to, after reacting 1h, room temperature is down to, forms intermediate M5；

2, continue that 40g polypropylene glycol (molecular weight 1000) is added into reaction kettle, and open and be uniformly mixed to get poly- Close object defoaming agent N5.

Embodiment 2-6

1, by the 39g hydrophilic fume colloidal silica of acrylate copolymer K6 and 15g (specific surface area 400m²/ g) it is added to instead It answers in kettle, after mixing evenly, is warming up to 50 DEG C, the 1g catalyst H6 (first that 5g potassium hydroxide is 400mPa.s with 95g viscosity is added Base silicone oil is obtained in 60 DEG C of reaction 1h), 100 DEG C are warming up to, after reacting 1h, room temperature is down to, forms intermediate M6；

2, continuing addition 25gPPG800,20g aliphatic alcohol polyether into reaction kettle, (fatty alcohol is initiator, and molecular weight is 2000, EO and PO copolymer), and open and be uniformly mixed to get polymer defoaming agent N6.

Embodiment 2-7

1, by the 33g hydrophilic fume colloidal silica of acrylate copolymer K7 and 0.5g (specific surface area 150m²/ g) it is added to In reaction kettle, after mixing evenly, 50 DEG C are warming up to, 1.5g catalyst H7 is added, and (5g potassium hydroxide is 10mPa.s with 95g viscosity Methyl-silicone oil obtained in 50 DEG C of reaction 0.5h), be warming up to 100 DEG C, after reacting 1h, be down to room temperature, form intermediate M7；

2, continue that 65gPPG300 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N7.

Embodiment 2-8

1, by the 40g hydrophilic fume colloidal silica of acrylate copolymer K8 and 9.5g (specific surface area 300m²/ g) it is added to In reaction kettle, after mixing evenly, 80 DEG C are warming up to, 0.5g catalyst H8 is added, and (5g sodium hydroxide is 1000mPa.s with 95g viscosity Methyl-silicone oil obtained in 80 DEG C of reaction 3h), be warming up to 90 DEG C, after reacting 2h, be down to room temperature, form intermediate M8；

2, continue that 50gPPG1000 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N8.

Embodiment 2-9

1, by the 50g hydrophilic fume colloidal silica of acrylate copolymer K9 and 12g (specific surface area 300m²/ g) it is added to instead It answers in kettle, after mixing evenly, is warming up to 50 DEG C, the 3g catalyst H9 (first that 5g sodium hydroxide is 600mPa.s with 95g viscosity is added Base silicone oil is obtained in 70 DEG C of reaction 2h), 100 DEG C are warming up to, after reacting 1h, room temperature is down to, forms intermediate M9；

2, continue into reaction kettle be added 40g polypropylene glycol (molecular weight 1000), and open be uniformly mixed to get Polymer defoaming agent N9.

Embodiment 2-10

1, by the 10g hydrophilic fume colloidal silica of acrylate copolymer K10 and 10g (specific surface area 200m²/ g) it is added to In reaction kettle, after mixing evenly, 60 DEG C are warming up to, 5g catalyst H10 is added, and (5g potassium hydroxide and 95g viscosity is 40mPa.s' Methyl-silicone oil is obtained in 60 DEG C of reaction 0.5h), 95 DEG C are warming up to, after reacting 1.5h, room temperature is down to, forms intermediate M10；

2, continue that 75gPPG2000 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N10.

Embodiment 2-11

1, by the 19.8g hydrophilic fume colloidal silica of acrylate copolymer K11 and 0.1g (specific surface area 250m²/ g) it is added Into reaction kettle, after mixing evenly, it is warming up to 70 DEG C, 0.1g catalyst H4 is added, and (5g potassium hydroxide is with 95g viscosity The methyl-silicone oil of 300mPa.s is obtained in 60 DEG C of reaction 1h), 95 DEG C are warming up to, after reacting 2h, room temperature is down to, forms intermediate M11；

2, continue into reaction kettle be added 80g polyethylene glycol (molecular weight 1000), and open be uniformly mixed to get Polymer defoaming agent N11.

Embodiment 2-12

1, by the 39g hydrophilic fume colloidal silica of acrylate copolymer K12 and 15g (specific surface area 400m²/ g) it is added to In reaction kettle, after mixing evenly, 50 DEG C are warming up to, 1g catalyst H6 is added, and (5g potassium hydroxide and 95g viscosity is 400mPa.s' Methyl-silicone oil is obtained in 60 DEG C of reaction 1h), 100 DEG C are warming up to, after reacting 1h, room temperature is down to, forms intermediate M12；

2, continue that 45g isooctanol is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N12.

Embodiment 2-13

1, by the 40g hydrophilic fume colloidal silica of acrylate copolymer K13 and 9.5g (specific surface area 500m²/ g) it is added to In reaction kettle, after mixing evenly, 80 DEG C are warming up to, 0.5g catalyst H2 is added, and (5g potassium hydroxide is 500mPa.s with 95g viscosity Methyl-silicone oil obtained in 60 DEG C of reaction 1h), be warming up to 90 DEG C, after reacting 2h, be down to room temperature, form intermediate M13；

2, continue that 50g hexanedioic acid dioctyl ester is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming Agent N13.

Embodiment 2-14

1, by the 19.8g hydrophilic fume colloidal silica of acrylate copolymer K14 and 0.1g (specific surface area 250m²/ g) it is added Into reaction kettle, after mixing evenly, it is warming up to 70 DEG C, 0.1g catalyst H4 is added, and (5g potassium hydroxide is with 95g viscosity The methyl-silicone oil of 300mPa.s is obtained in 60 DEG C of reaction 1h), 95 DEG C are warming up to, after reacting 2h, room temperature is down to, forms intermediate M14；

2, continue that 80g polybutene (molecular weight 500) is added into reaction kettle, and open and be uniformly mixed to get polymerization Object defoaming agent N14.

Embodiment 2-15

1, by the 39g hydrophilic fume colloidal silica of acrylate copolymer K15 and 15g (specific surface area 400m²/ g) it is added to In reaction kettle, after mixing evenly, 50 DEG C are warming up to, 1g catalyst H6 is added, and (5g potassium hydroxide and 95g viscosity is 400mPa.s' Methyl-silicone oil is obtained in 60 DEG C of reaction 1h), 100 DEG C are warming up to, after reacting 1h, room temperature is down to, forms intermediate M15；

2, continue that 45g polytetramethylene glycol (molecular weight 800) is added into reaction kettle, and open and be uniformly mixed to get poly- Close object defoaming agent N15.

Comparative example 2-1

1, by the 20g hydrophilic fume colloidal silica of acrylate copolymer K-1 and 8g (specific surface area 150m²/ g) it is added to instead It answers in kettle, after mixing evenly, is warming up to 50 DEG C, the 2g catalyst H1 (first that 5g potassium hydroxide is 50mPa.s with 95g viscosity is added Base silicone oil is obtained in 60 DEG C of reaction 1h), 100 DEG C are warming up to, after reacting 1h, room temperature is down to, forms intermediate M-1；

2, continue that 70gPPG300 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N-1.

Comparative example 2-2

1, by the 40g hydrophilic fume colloidal silica of acrylate copolymer K-2 and 9.5g (specific surface area 500m²/ g) it is added to In reaction kettle, after mixing evenly, 80 DEG C are warming up to, 0.5g catalyst H2 is added, and (5g potassium hydroxide is 500mPa.s with 95g viscosity Methyl-silicone oil obtained in 60 DEG C of reaction 1h), be warming up to 90 DEG C, after reacting 2h, be down to room temperature, form intermediate M-2；

2, continue that 50gPPG1000 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N-2.

Comparative example 2-3

1, by the 10g hydrophilic fume colloidal silica of acrylate copolymer K-3 and 10g (specific surface area 200m²/ g) it is added to In reaction kettle, after mixing evenly, 60 DEG C are warming up to, 5g catalyst H3 is added, and (5g potassium hydroxide and 95g viscosity is 100mPa.s' Methyl-silicone oil is obtained in 60 DEG C of reaction 1h), 95 DEG C are warming up to, after reacting 1.5h, room temperature is down to, forms intermediate M-3；

2, continue that 75gPPG2000 is added into reaction kettle, and open and be uniformly mixed to get polymer defoaming agent N-3.

Comparative example 2-4

1, by the 19.8g hydrophilic fume colloidal silica of acrylate copolymer K4 and 0.2g (specific surface area 250m²/ g) it is added Into reaction kettle, after mixing evenly, intermediate M-4 is formed；

2, continuing the addition 50g aliphatic alcohol polyether into reaction kettle, (fatty alcohol is initiator, molecular weight 300, EO, PO copolymerization Object), 30gPPG1000, and open be uniformly mixed to get polymer defoaming agent N-4.

Comparative example 2-5

It is compared with embodiment C23 in patent CN101189282B, mainly using silicone grease and silicon polyethers in embodiment C23 Compounding prepares defoaming agent N- V.It is specific as follows:

Comparative example 2-6

1, by 50g acrylate copolymer (polymer prepared referring to embodiment 1 in patent CN102428142B) and 12g parent Water fume colloidal silica (specific surface area 300m²/ g) it is added in reaction kettle, after mixing evenly, 50 DEG C are warming up to, 3g is added Catalyst H5 (5g potassium hydroxide reacts 1h at 60 DEG C with the methyl-silicone oil that 95g viscosity is 300mPa.s and obtains), is warming up to 100 DEG C, after reacting 1h, it is down to room temperature, forms intermediate M-6；

2, continue that 40g polypropylene glycol (molecular weight 1000) is added into reaction kettle, and open and be uniformly mixed to get poly- Close object defoaming agent N-6.

The performance test test method for the foam inhibition that disappears

To having in the circulation bubbling instrument of 0~500mL of scale and internal diameter for the glass tube of 5cm, 600mL papermaking system is added Black liquor is starched, reaches its liquid level at minimum scale " 0mL ", then set temperature is 80 DEG C, flow 6L/min, voltage 220V, Then temperature detect switch (TDS) is opened, opens circulating pump after paper-making pulping black liquor is heated to set temperature, starts impact blistering, to foam It is raised at 350mL, the defoaming agent of 0.2ml is added, record foam height changes with time.Foam reaches the time of minimum scale It is shorter, and the scale reached is lower, illustrates that the moment antifoam performance of defoaming agent is better；Reach again in foam and passes through at 350mL Time it is longer, illustrate that the suds suppressing properties of defoaming agent are better.

Embodiment 3-1~embodiment 3-5 is all made of this method and is tested for the property

Embodiment 3-1

The defoaming agent of embodiment 2-1~embodiment 2-9, comparative example 2-1~comparative example 2-6 preparation disappear the property of foam inhibition It can test, test result is as shown in table 1:

1 antifoaming performance test result of table

By above data as can be seen that compared to monomer, alkene is not the polymer defoaming that preparation is added dropwise by substep Agent N- I, defoaming agent N1-N9 of the present invention improve the moment defoaming capacity and later period foam inhibition ability of defoaming agent；Compared to molecular weight Polymer the defoaming agent N-2, defoaming agent N1-N9 of the acrylate copolymer preparation of < 15000 further improve foam inhibition ability；Phase Polymer defoaming agent N-3, defoaming agent N1-N9 than the acrylate copolymer preparation in molecular weight > 30000 substantially increase wink Between defoaming capacity and foam inhibition ability；It is not to carry out the polymer that hydroxyl condensation reacts preparation with polymer compared to hydrophilic white carbon black Defoaming agent N-4, defoaming agent N1-N9 are further defoamed and foam inhibition ability；Compared to it is existing with silicone grease etc. for the organic of active matter Silicon defoaming agent N-5, defoaming agent N1-N9 increase significantly in moment defoaming capacity, foam inhibition ability；Compared to existing propylene Polymer the defoaming agent N-6, defoaming agent N1-N9 of acid esters preparation are by with alkyl acrylate, alkyl methacrylate, third On the basis of olefin(e) acid hydroxy alkyl ester is monomer, by specific process polymerisation, and after being modified with special Long carbon chain monomer, together When control polymer molecular weight 15000~30000, effectively raise the later period foam inhibition ability of polymer；Then with parent Water-white carbon black carries out hydroxyl condensation under alkaline condition, carries out modification again to polymer, significantly more efficient to improve polymerization The defoaming capacity of object.

Embodiment 3-2

Method with embodiment 2-1 prepares polymer defoaming agent, changes acrylate polymer, organic solvent carriers, nothing Machine filler, the additive amount of catalyst investigate its influence to polymer defoaming agent performance；

Influence of the composition of 2 polymer defoaming agent of table to antifoaming performance

Embodiment 3-3

Method with embodiment 2-1 prepares polymer defoaming agent, changes the additive amount of acrylate copolymer K1 raw material components, Investigate its influence to polymer defoaming agent performance；

Influence of the additive amount of 3 acrylate copolymer raw material components of table to antifoaming performance

Embodiment 3-4

Method with embodiment 2-1 prepares polymer defoaming agent, changes the selection of acrylate copolymer K1 raw material components, examines Examine its influence to polymer defoaming agent performance；

Influence of the selection of 4 acrylate copolymer raw material components of table to antifoaming performance

Embodiment 3-5

Method with embodiment 2-1 prepares polymer defoaming agent, changes the selection of polymer component of antifoam agent, it is right to investigate its The influence of polymer defoaming agent performance；

Influence of the selection of 5 polymer component of antifoam agent of table to antifoaming performance

It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.

Claims

1. a kind of polymer defoaming agent, which is characterized in that including acrylate polymer, organic solvent carriers, inorganic filler, urge Agent；The dosage of the acrylate polymer accounts for the 10~50% of defoaming agent gross mass, the organic solvent carriers Dosage accounts for the 40~80% of defoaming agent gross mass, and the dosage of the inorganic filler accounts for the 0.1~15% of defoaming agent gross mass, institute The dosage for the catalyst stated accounts for the 0.1-5% of defoaming agent gross mass；

The acrylate polymer is made of following raw material components: monomer -1, monomer -2, monomer -3, alkene, dilution Agent, initiator, chain-transferring agent；The monomer -1 is alkyl acrylate；The monomer -2 is alkyl methacrylate； The monomer -3 is acrylic acid hydroxy alkyl ester.

2. polymer defoaming agent as described in claim 1, which is characterized in that the dosage of the acrylate polymer, which accounts for, to disappear The 20~40% of infusion gross mass, the dosage of the organic solvent carriers accounts for the 50~70% of defoaming agent gross mass, described The dosage of inorganic filler accounts for the 0.5~10% of defoaming agent gross mass, and the dosage of the catalyst accounts for the 0.5 of defoaming agent gross mass ~2%.

3. polymer defoaming agent as described in claim 1, which is characterized in that the molecular weight of the acrylate polymer exists Between 15000~30000.

4. polymer defoaming agent as described in claim 1, which is characterized in that the monomer -1, monomer -2 and monomer -3 Total dosage accounts for the 30~70% of acrylate polymer raw material components gross mass, and the dosage of the alkene accounts for polymer raw material group Divide the 0.5~5% of gross mass, the dosage of the diluent accounts for the 25~65% of polymer raw material component gross mass, described The dosage of initiator accounts for the 0.2~1% of polymer raw material component gross mass, and the dosage of the chain-transferring agent accounts for polymer raw material The 0.1~1% of component gross mass.

5. polymer defoaming agent as described in claim 1, which is characterized in that the monomer -1, monomer -2, monomer -3 it is total Dosage accounts for the 40~60% of acrylate polymer raw material components gross mass, and the dosage of the alkene accounts for polymer raw material component The 1~4% of gross mass；The dosage of the diluent accounts for the 35~55% of polymer raw material component gross mass；The initiation The dosage of agent accounts for the 0.4~0.8% of polymer raw material component gross mass, and the dosage of the chain-transferring agent accounts for polymer raw material group Divide the 0.2~0.6% of gross mass.

6. polymer defoaming agent as described in claim 1, which is characterized in that the monomer -1 account for monomer gross mass 60~ 80%, monomer -2 accounts for the 5~15% of monomer gross mass, and monomer -3 accounts for the 10~30% of monomer gross mass.

7. polymer defoaming agent as described in claim 1, which is characterized in that wherein monomer -1 account for monomer gross mass 65~ 75%, monomer -2 accounts for the 8~12% of monomer gross mass, and monomer -3 accounts for the 15~25% of monomer gross mass.

8. polymer defoaming agent as described in claim 1, which is characterized in that the monomer -1 is selected from methyl acrylate, propylene Acetoacetic ester, butyl acrylate, dodecyl acrylate, octadecyl acrylate, Isooctyl acrylate monomer.

9. polymer defoaming agent as described in claim 1, which is characterized in that the monomer -2 be selected from methyl methacrylate, Ethyl methacrylate, butyl methacrylate, lauryl methacrylate, octadecyl methacrylate, methacrylic acid are different Monooctyl ester.

10. polymer defoaming agent as described in claim 1, which is characterized in that the monomer -3 is as shown in following general formula Acrylic acid hydroxy alkyl ester:

Wherein R is selected from 1- hydroxyethyl, 2- ethoxy, 1- hydroxypropyl, 2- hydroxypropyl, 3- hydroxypropyl, 1- hydroxyisopropyl, 2- hydroxyl Base isopropyl, 3- hydroxyisopropyl, 1- hydroxyl butyl, 2- hydroxyl butyl, 3- hydroxyl butyl or 4- hydroxyl butyl.

11. polymer defoaming agent as described in claim 1, which is characterized in that the monomer -1 is Isooctyl acrylate monomer；Institute The monomer -2 stated is lauryl methacrylate；The monomer -3 is hydroxy-ethyl acrylate.

12. polymer defoaming agent as described in claim 1, which is characterized in that the alkene is as shown in following general formula:

CH₂=CHR¹

Wherein R¹For the linear or branched alkyl group of 4~20 carbon atoms.

13. polymer defoaming agent as claimed in claim 12, which is characterized in that R¹For the direct-connected alkyl of 10~16 carbon atoms.

14. polymer defoaming agent as described in claim 1, which is characterized in that it is different that the diluent is selected from phthalic acid two Last of the ten Heavenly stems ester, diisooctyl adipate, diisooctyl phthalate, dioctyl adipate, 2- ethyl -1- hexanol, isooctanol, molecule Measure the polybutadiene that the polyethylene glycol for 300~2000, the polypropylene glycol that molecular weight is 300~2000, molecular weight are 300~2000 The mixing of any one or a few in alcohol, the aliphatic alcohol polyether that molecular weight is 300-2000.

15. polymer defoaming agent as described in claim 1, which is characterized in that the diluent be molecular weight be 300~ 2000 polypropylene glycol and/or molecular weight is the aliphatic alcohol polyether of 300-2000.

16. polymer defoaming agent as described in claim 1, which is characterized in that the initiator is double selected from 2,2 '-azos (2- methyl propionitrile), 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2- methylbutyronitriles), benzoyl peroxide first Acyl, bromate/sulfide systems, persulfate/ferrous iron system.

17. polymer defoaming agent as described in claim 1, which is characterized in that the initiator is benzoyl peroxide.

18. polymer defoaming agent as described in claim 1, which is characterized in that the chain-transferring agent is lauryl mercaptan.

19. polymer defoaming agent as described in claim 1, which is characterized in that the solvent carrier is selected from phthalic acid Diisodecyl ester, diisooctyl adipate, diisooctyl phthalate, adipic acid dibutyl ester, 2- ethyl -1- hexanol, isooctanol, The poly- second that polybutene that polytetramethylene glycol that molecular weight is 300~2000, molecular weight are 400~2000, molecular weight are 300~2000 Glycol or its polyether ester formed with fatty acid, the polypropylene glycol that molecular weight is 300~2000 or its formed with fatty acid it is poly- Ether-ether, molecular weight are the mixing of any one or a few in the aliphatic alcohol polyether of 300-2000.

20. polymer defoaming agent as described in claim 1, which is characterized in that the organic solvent carriers are that molecular weight is 300 ~2000 polypropylene glycol and/or molecular weight is the aliphatic alcohol polyether of 300-2000.

21. polymer defoaming agent as described in claim 1, which is characterized in that the inorganic filler is that specific surface area is 150 ~500m²The hydrophilic fume colloidal silica of/g.

22. polymer defoaming agent as described in claim 1, which is characterized in that the catalyst is by sodium hydroxide or hydrogen Potassium oxide is made with methyl-silicone oil agitating and heating.

23. polymer defoaming agent as claimed in claim 22, which is characterized in that the condition of the agitating and heating are as follows: heating temperature Degree is 50~80 DEG C, and mixing time is 0.5~3h.

24. polymer defoaming agent as claimed in claim 22, which is characterized in that the dosage of the sodium hydroxide or potassium hydroxide It is the 5% of catalyst gross mass, the dosage of methyl-silicone oil is the 95% of catalyst gross mass.

25. polymer defoaming agent as claimed in claim 22, which is characterized in that the methyl-silicone oil viscosity be 10~ 1000mPa.s。

26. polymer defoaming agent as described in claim 1, which is characterized in that the catalyst is by potassium hydroxide and to glue Degree is that the methyl-silicone oil of 50~500mPa.s is warming up to 60 DEG C, and continues stirring 1h and be prepared.

27. a kind of preparation method of acrylate polymer, which comprises the following steps:

(1) alkyl acrylate, alkyl methacrylate, acrylic acid hydroxy alkyl ester and initiator are mixed, is stirred evenly It is completely dissolved initiator, forms mixture a；

(2) alkene is mixed with initiator, stirring evenly is completely dissolved initiator, forms mixture b；

(3) initiator is added in diluent and chain-transferring agent stirs evenly, until initiator is completely dissolved, form mixture c；

(4) under the conditions of 90~100 DEG C, initiator, reaction is added in the alternate dropwise addition mixture a and mixture b into mixture c Generate mixture j；

(5) the mixture j, which cleans, is made acrylate polymer.

28. the preparation method of acrylate polymer as claimed in claim 27, which is characterized in that in the step (4), mix Object a and mixture b is closed to be added dropwise in three times.

29. the preparation method of acrylate polymer as claimed in claim 27, which is characterized in that in the step (5), remove Miscellaneous method are as follows: mixture j distills 0.5~3h at vacuum degree -0.09~-0.1MPa, 90~110 DEG C of temperature.

30. the preparation method of polymer defoaming agent as described in claim 1, which comprises the following steps:

Step 1, acrylate copolymer and inorganic filler are added in reaction kettle, stir evenly and be warming up to 50~80 DEG C, so After catalyst is added, and be warming up to 90~100 DEG C, react 1-2h；Then it is down to room temperature, forms intermediate；

Step 2, continue that organic solvent carriers are added into reaction kettle, be uniformly mixed, the polymer defoaming agent is made.

31. as the described in any item polymer defoaming agents of claim 1-30 be in alkali system paper-making pulping system defoaming, It is applied in foam inhibition.