WO2021189393A1 - 一种聚合物乳液型消泡剂及其制备方法 - Google Patents

一种聚合物乳液型消泡剂及其制备方法 Download PDF

Info

Publication number
WO2021189393A1
WO2021189393A1 PCT/CN2020/081539 CN2020081539W WO2021189393A1 WO 2021189393 A1 WO2021189393 A1 WO 2021189393A1 CN 2020081539 W CN2020081539 W CN 2020081539W WO 2021189393 A1 WO2021189393 A1 WO 2021189393A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylate
preparation
defoamer
polymer emulsion
emulsion type
Prior art date
Application number
PCT/CN2020/081539
Other languages
English (en)
French (fr)
Inventor
李安宁
董飞
杨有忠
黄伟
曹添
K.达西 安东尼
Original Assignee
江苏四新科技应用研究所股份有限公司
南京绿界新材料研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江苏四新科技应用研究所股份有限公司, 南京绿界新材料研究院有限公司 filed Critical 江苏四新科技应用研究所股份有限公司
Publication of WO2021189393A1 publication Critical patent/WO2021189393A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/12—Defoamers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the invention relates to a polymer emulsion type defoamer and a preparation method.
  • the polymer emulsion is an important fine chemical additive. Therefore, the present invention belongs to the technical field of fine chemical preparations.
  • Papermaking is a key industry in the production of the national economy.
  • surfactants such as defoamers
  • Foams in most industrial production can bring great harm, such as reducing the efficiency of the machine, delaying labor time, and affecting the quality of the final product.
  • the method to eliminate harmful foam generally adopts the addition of defoaming agent.
  • the defoaming agent is divided into several main types, such as non-silicon type and organic silicon type. Compared with other defoamers, silicone defoamers have stable chemical properties, stable chemical resistance, and low side effects.
  • Non-silicon defoamer is based on mineral oil, polyether, amide or fatty alcohol, acrylate as the active substance. When used in large quantities, the active substance amide will gradually aggregate, condense, and leave spots on the paper; and mineral oil Under long-term high temperature conditions, tetrachlorodibenzo-p-dioxin (TCDD) harmful substances will be produced, which endangers personal safety and environmental safety. Silicone defoamers use polysiloxanes, fillers, etc. as active substances. Long-term use will cause the agglomeration of hydrophobic particles, which will then adhere to the paper and form silicon spots, which will reduce the quality of the paper.
  • TCDD tetrachlorodibenzo-p-dioxin
  • Patent US5152925A introduces a defoamer with a polyacrylate as the main defoaming active material.
  • the acrylate polymer is mainly composed of acrylate monomers containing hydroxyl in the solvent diisodecyl phthalate (DIDP) Or acrylate polymers prepared in solvents such as DIOP are used as the main active material to be used in papermaking black liquor washing and other papermaking processes.
  • DIDP solvent diisodecyl phthalate
  • Patent CN102428142B also mentions that acrylate polymers are used as active substances to prepare bulk defoamers.
  • the acrylate polymers are made of monomers such as isooctyl acrylate, hydroxy acrylate and acrylic acid in polybutene or polyether solvents.
  • the prepared acrylate polymer is used as the main active ingredient of the defoaming agent, and it is compounded with white carbon black, alkyl silicone oil and other defoaming additives. It is used in petroleum exploration, water treatment, coating industry and ink, food and Beverage processing, drilling industry, textile industry, papermaking and other industries. The emergence of such defoamers can solve the problem of silicon precipitation and residues of traditional silicone defoamers, but there is still much room for improvement in the defoaming performance of defoamers prepared by the current technology. Therefore, it is of great significance to improve the defoaming and suppressing properties of acrylate polymer defoamers.
  • the present invention solves the above-mentioned existing problems and proposes an emulsion type defoamer based on a polymer as an active substance. Advantages of the present invention:
  • a self-emulsifying polymer polymer is formed through the double bond addition reaction, which is adjusted by the content of the catalyst and the reaction time
  • the size of the molecular weight makes it have a certain range of viscosity, which can be emulsified in water to form emulsions with different particle size ranges.
  • the allyl polyether introduced into the high molecular polymer uses (OCH 2 CH 2 ) a and (OCH 2 CHCH 3 ) b in its structure to adjust the hydrophilic and hydrophobic balance (HLB) of the molecular structure,
  • the increase of (OCH 2 CH 2 ) a can significantly improve the hydrophilic properties
  • (OCH 2 CHCH 3 ) b can adjust the hydrophobic properties, so as to realize the self-emulsification of the molecular structure to form an emulsion.
  • allyl polyether has a low viscosity, which not only acts as a reaction monomer, but also realizes the role of reaction solvent, which solves the environmental protection problem caused by the use of toluene and other harmful solvents in the traditional acrylate synthesis process
  • the polymer emulsion can realize self-emulsification to form an emulsion, it solves a series of problems such as oil bleaching, precipitation and demulsification caused by the use of some emulsifiers in traditional silicone emulsion defoamers.
  • a polymer emulsion type defoamer consists of the following components: active matter accounts for 10-35% of the total mass of the defoamer, filler particles account for 3-8% of the total mass of the defoamer, and water accounts for the total mass of the defoamer 60-85%, thickener accounts for 0.5-3% of the total mass of defoamer;
  • the active material is composed of acrylate, allyl polyether, and a catalyst, wherein the acrylate accounts for 29-70% of the total mass of the active material, and the allyl polyether It accounts for 29-70% of the total mass of the active material, and the catalyst accounts for 0.5-2% of the total mass of the active material;
  • a polymer emulsion type defoaming agent and a preparation method wherein the acrylate is selected from hydroxyethyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, stearyl acrylate, and isooctyl acrylate One or more than two kinds of mixed in any ratio;
  • a polymer emulsion type defoaming agent and a preparation method are selected from hydrophobic white carbon black, titanium dioxide, magnesium oxide, aluminum oxide, ethylenediamine bisstearic acid amide (EBS), and aluminum stearate.
  • EBS ethylenediamine bisstearic acid amide
  • the specific surface area of the filler particles in a polymer emulsion type defoamer and its preparation method is 150-500 m 2 /g;
  • a polymer emulsion type defoaming agent and the preparation method thereof is polyacrylamide, carbomer, xanthan gum, polyacrylate, methyl cellulose, carboxymethyl cellulose, and hydroxyethyl One or more of cellulose and ethyl cellulose;
  • a polymer emulsion type defoamer and a preparation method thereof A polymer emulsion type defoamer and a preparation method thereof.
  • the general structural formula of the allyl polyether A is as follows:
  • CH 2 CHCH 2 (OCH 2 CH 2 ) a (OCH 2 CHCH 3 ) b, where a is an integer of 1-10, and b is an integer of 10-100.
  • a polymer emulsion type defoamer and a preparation method thereof is selected from the group consisting of 2,2'-azobis(2-methylpropionitrile), tert-butyl peroxide 2-ethylhexyl acid, and tertiary peroxide Butyl, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), one of benzoyl peroxide;
  • a preparation method of polymer emulsion type defoamer includes the following steps:
  • sample A-sample I Using self-prepared cork liquid, test the anti-foaming performance of sample A-sample I in a circulating bubbler. Inject 600mL of cork liquid into a rigid glass cylinder with an inner diameter of 5cm in the circulating bubbler, increase the temperature and maintain it at 80°C, turn on the liquid circulation switch, and control the flow rate to 6L/min. When the foam height in the glass cylinder rises to 300mL, Inject 0.4mL of defoamer and start timing, while recording the foam height until the foam height rises to 300 mL again, and stop the liquid circulation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本发明提供了一种聚合物乳液型消泡剂及其制备方法，组分包括活性物、填料粒子、水、增稠剂，其中活性物由丙烯酸酯，烯丙基聚醚，催化剂组成，通过在丙烯酸酯聚合物链段中引入含有亲水官能团的烯丙基聚醚，合成过程中烯丙基聚醚的引入解决了传统丙烯酸酯合成过程中使用甲苯等有害溶剂带来的环保问题；双键加成反应形成一种自乳化功能的聚合物高分子，可在水中进行乳化，形成不同粒径范围的乳液；聚合物乳液由于自身可实现自乳化形成乳液，解决了传统有机硅乳液型消泡剂使用一些乳化剂所带来的漂油，析出，破乳等一系列问题。

Description

一种聚合物乳液型消泡剂及其制备方法 技术领域
本发明涉及一种聚合物乳液型消泡剂及制备方法，聚合物乳液是重要精细化学品添加剂，因此，本发明隶属于精细化工制剂技术领域。
背景技术
造纸是国民经济生产中的重点工业。在造纸工业中，常常用到多种表面活性剂，例如消泡剂。绝大多数工业生产中泡沫会带来极大的危害，例如降低机器的工作效率、延误劳动时间、影响最终产品的质量等。消除有害泡沫的方法一般采用添加消泡剂.消泡组合物的不同，消泡剂分为非硅型和有机硅类等几种主要类型。与其他消泡剂相比，有机硅类消泡剂化学性能稳定，耐化学品稳定，副作用小，同时在用量很低的情况下也有很好的消泡瞬间消泡能力，因而，很受青睐.而非硅消泡剂是以矿物油、聚醚、酰胺或脂肪醇、丙烯酸酯为活性物，在大量的使用时，活性物酰胺会逐渐聚集，凝结，在纸张上残留斑点；且矿物油在长时间的高温情况下会产生四氯二苯并-p-二恶英(TCDD)有害物质，危害人身安全及环境安全。有机硅消泡剂是以聚硅氧烷、填料等为活性物，长时间的使用会导致疏水粒子的团聚，后附着在纸张上，形成硅斑，造成纸张质量下降。
专利US5152925A介绍的是以一种聚丙烯酸酯作为主要消泡活性物质的消泡剂，其中丙烯酸酯聚合物主要以含有羟基的丙烯酸酯类单体在溶剂邻苯二甲酸二异癸酯(DIDP)或DIOP等溶剂中制备的丙烯酸 酯聚合物作为主要活性物质，应用于造纸黑液洗涤和其他造纸工序。专利CN102428142B中同样提到以丙烯酸酯聚合物作为活性物质制备本体型消泡剂，其中丙烯酸酯聚合物由丙烯酸异辛酯、丙烯酸羟基酯以及丙烯酸等单体在聚丁烯或聚醚溶剂等中制备，将制备的丙烯酸酯聚合物作为消泡剂的主要活性成分，并和白炭黑、烷基硅油等消泡助剂复配，应用于石油开采、水处理、涂料工业和油墨、食品和饮料加工、钻井业、纺织业、造纸等行业。此类消泡剂的出现可以解决传统有机硅消泡剂硅析出残留问题，但是目前技术制备的消泡剂消抑泡性能仍有很大的提升空间。因此，提高丙烯酸酯聚合物消泡剂的消抑泡性能将有重要意义。
发明内容
本发明解决上述存在的问题，提出一种基于聚合物为活性物的乳液型消泡剂。本发明的优势：
(1)通过在丙烯酸酯聚合物链段中引入含有亲水官能团的烯丙基聚醚，通过双键加成反应形成一种自乳化功能的聚合物高分子，通过催化剂的含量和反应时间调整分子量的大小，使其具有一定范围的粘度，可在水中进行乳化，形成不同粒径范围的乳液。
(2)高分子聚合物中所引入的烯丙基聚醚，利用其结构中(OCH 2CH 2) a和(OCH 2CHCH 3) b对分子结构进行调整亲水疏水平衡值(HLB)，(OCH 2CH 2) a增加可显著改善亲水性能，(OCH 2CHCH 3) b可调节疏水性能,从而实现分子结构的自乳化形成乳液。
(3)在合成过程中，烯丙基聚醚粘度较小，既作为反应单体，又实现了反应溶剂的作用，解决了传统丙烯酸酯合成过程中使用甲苯等有害溶剂带来的环保问题
(4)聚合物乳液由于自身可实现自乳化形成乳液，解决了传统有机硅乳液型消泡剂使用一些乳化剂所带来的漂油，析出，破乳等一系列问题。
为实现上述效果，本发明的一种聚合物乳液型消泡剂及制备方法技术方案如下：
一种聚合物乳液型消泡剂由以下组分组成：活性物占消泡剂总质量的10-35％，填料粒子占消泡剂总质量的3-8％，水占消泡剂总质量的60-85％，增稠剂占消泡剂总质量的0.5-3％；
一种聚合物乳液型消泡剂及其制备方法，所述活性物由丙烯酸酯，烯丙基聚醚，催化剂组成，其中丙烯酸酯占活性物总质量的29-70％，烯丙基聚醚占活性物总质量的29-70％，催化剂占活性物总质量的0.5-2％；
一种聚合物乳液型消泡剂及制备方法，所述丙烯酸酯选自丙烯酸羟乙酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸十八酯、丙烯酸异辛酯中的一种或两种以上任意比例混合；
一种聚合物乳液型消泡剂及制备方法，所述填料粒子选自疏水白炭黑、二氧化钛、氧化镁、氧化铝、乙二胺双硬脂酸酰胺(EBS)、硬脂酸铝中的一种或几种；
一种聚合物乳液型消泡剂及制备方法中所述填料粒子比表面积 为150～500m 2/g；
一种聚合物乳液型消泡剂及其制备方法中所述增稠剂为聚丙烯酰胺、卡波姆、汉生胶、聚丙烯酸酯、甲基纤维素、羧甲基纤维素、羟乙基纤维素、乙基纤维素中一种或几种；
一种聚合物乳液型消泡剂及制备方法，所述烯丙基聚醚A的结构通式如下：
CH 2＝CHCH 2(OCH 2CH 2) a(OCH 2CHCH 3) b其中a为1-10整数，b为10-100整数。
一种聚合物乳液型消泡剂及制备方法，所述催化剂选自2,2’-偶氮双(2-甲基丙腈)，过氧化2-乙基己基酸叔丁酯，过氧化叔丁基，2,2’-偶氮双(2,4-二甲基戊腈)，2,2’-偶氮双(2-甲基丁腈)、过氧化苯甲酰中一种；
一种聚合物乳液型消泡剂制备方法，包括以下步骤：
(1)活性物的制备：将丙烯酸酯，催化剂加入烧瓶中，搅拌时间30-90min，将上述混合物滴入含有烯丙基聚醚的反应器中，反应温度60-100℃，滴加反应时间为2-8h；
(2)将活性物，填料粒子，增稠剂置于高速搅拌器中，搅拌速度为1500-2500rpm，缓慢滴入水，搅拌时间30-120min后，得到聚合物乳液消泡剂。
具体实施例
实施例一、
(1)活性物的制备：将10g丙烯酸羟乙酯、19g丙烯酸异辛酯、1g催化剂2,2’-偶氮双(2-甲基丙腈)加入烧瓶中，搅拌时间30min，将上述混合物滴入含有70g烯丙基聚醚CH 2＝CHCH 2(OCH 2CH 2)(OCH 2CHCH 3) 100的反应器中，反应温度60℃，滴加反应时间为8h；
(2)将10g活性物、8g疏水白炭黑(比表面积为150m 2/g)、1g聚丙烯酰胺、2g聚丙烯酸酯置于高速搅拌器中，搅拌速度为1500rpm，缓慢滴入79g的水，搅拌时间120min后，得到聚合物乳液消泡剂，记为A。
实施例二、
(1)活性物的制备：将70g丙烯酸乙酯，1g催化剂过氧化2-乙基己基酸叔丁酯加入烧瓶中，搅拌时间90min，将上述混合物滴入含有29g烯丙基聚醚CH 2＝CHCH 2(OCH 2CH 2) 10(OCH 2CHCH 3) 10的反应器中，反应温度100℃，滴加反应时间为2h；
(2)将35g活性物，3g二氧化钛(比表面积300m 2/g)，0.5g聚丙烯酰胺置于高速搅拌器中，搅拌速度为2500rpm，缓慢滴入61.5g的水，搅拌时间30min后，得到聚合物乳液消泡剂，记为B。
实施例三、
(1)活性物的制备：将10g丙烯酸月桂酯、35g丙烯酸丁酯，0.5g催化剂过氧化苯甲酰加入烧瓶中，搅拌时间60min，将上述混合物滴入含有54.5g烯丙基聚醚CH 2＝CHCH 2(OCH 2CH 2) 5(OCH 2CHCH 3) 50的反应器中，反应温度80℃，滴加反应时间为5h；
(2)将34g活性物，2g乙二胺双硬脂酸酰胺(比表面积为200m 2/g)，3g硬脂酸铝(比表面积为300m 2/g)，1g汉生胶置于高速搅拌器中，搅拌速度为2000rpm，缓慢滴入60g的水，搅拌时间80min后，得到聚合物乳液消泡剂，记为C。
实施例四、
(1)活性物的制备：将60g丙烯酸甲酯，5g丙烯酸十八酯，2g催化剂2,2’-偶氮双(2-甲基丁腈)加入烧瓶中，搅拌时间50min，将上述混合物滴入含有33g烯丙基聚醚CH 2＝CHCH 2(OCH 2CH 2) 8(OCH 2CHCH 3) 65的反应器中，反应温度70℃，滴加反应时间为4h；
(2)将10.5g活性物，1.5g卡波姆，1.5g氧化镁(比表面积为250m 2/g)，1.5g氧化铝(比表面积为300m 2/g)置于高速搅拌器中，搅拌速度为2300rpm，缓慢滴入85g的水，搅拌时间100min后，得到聚合物乳液消泡剂，记为D。
实施例五、
(1)活性物的制备：将10g丙烯酸羟乙酯，10g丙烯酸异辛酯，10g丙烯酸丁酯，1.5g过氧化叔丁基加入烧瓶中，搅拌时间40min，将上述混合物滴入含有48.5g烯丙基聚醚CH 2＝CHCH 2(OCH 2CH 2) 3(OCH 2CHCH 3) 32的反应器中，反应温度70℃，滴加反应时间为7h；
(2)将22g活性物，6g硬脂酸铝(比表面积为350m 2/g)，2g羧甲基纤维素置于高速搅拌器中，搅拌速度为1600rpm，缓慢滴入70g的水，搅拌时间50min后，得到聚合物乳液消泡剂，记为E。
对比例1-实施例1相对，去掉烯丙基聚醚
(1)活性物的制备：将40g丙烯酸羟乙酯、58g丙烯酸异辛酯、2g催化剂2,2’-偶氮双(2-甲基丙腈)加入烧瓶中，搅拌均匀，升温至反应温度60℃，反应时间为8h；
(2)将10g活性物、8g疏水白炭黑(比表面积为150m 2/g)、1g聚丙烯酰胺、2g聚丙烯酸酯置于高速搅拌器中，搅拌速度为1500rpm，缓慢滴入79g的水，搅拌时间120min后，得到聚合物消泡剂，记为F。
对比例2-实施例2相对，烯丙基聚醚的取值超过范围
(1)活性物的制备：将70g丙烯酸乙酯，1g催化剂过氧化2-乙基己基酸叔丁酯加入烧瓶中，搅拌时间90min，将上述混合物滴入含有29g烯丙基聚醚CH 2＝CHCH 2(OCH 2CH 2) 100(OCH 2CHCH 3) 200的反应器中，反应温度100℃，滴加反应时间为2h；
(2)将35g活性物，3g二氧化钛(比表面积300m 2/g)，0.5g聚丙烯酰胺置于高速搅拌器中，搅拌速度为2500rpm，缓慢滴入61.5g的水，搅拌时间30min后，得到聚合物消泡剂，记为G。
对比例3-与实施例3相对，烯丙基聚醚的取值超过范围
(1)活性物的制备：将10g丙烯酸月桂酯、35g丙烯酸丁酯，0.5g催化剂过氧化苯甲酰加入烧瓶中，搅拌时间60min，将上述混合物滴入含有54.5g烯丙基聚醚CH 2＝CHCH 2(OCH 2CH 2) 5(OCH 2CHCH 3) 3的反应器中，反应温度80℃，滴加反应时间为5h；
(2)将34g活性物，2g乙二胺双硬脂酸酰胺(比表面积为200 m 2/g)，3g硬脂酸铝(比表面积为300m 2/g)，1g汉生胶置于高速搅拌器中，搅拌速度为2000rpm，缓慢滴入60g的水，搅拌时间80min后，得到聚合物消泡剂，记为H。
对比例4-与普通有机硅乳液相对比
根据专利CN109929120A中实施例1制备，记为I。
消抑泡性能测试：
消泡剂性能对比测试方法如下
使用自配软木液，在循环鼓泡仪内测试样品A-样品I的消抑泡性能。将600mL软木液注入循环鼓泡仪中内径为5cm的硬质玻璃圆筒中，升温并维持在80℃，打开液体循环开关，控制流量至6L/min，当玻璃圆筒中泡沫高度上升至300mL时，注入0.4mL消泡剂并开始计时，同时记录泡沫高度，直至泡沫高度再次回升至300mL，停止液体循环。加入消泡剂后泡沫下降至250mL处的速度越快，最低泡沫高度越低，说明消泡性能越好；泡沫再次回升至300mL时所需时间越长说明消泡剂组合物抑泡性能越好。测试结果见表1。
表1.消泡剂性能对比
Figure PCTCN2020081539-appb-000001
Figure PCTCN2020081539-appb-000002
数据表1.，可以看出聚合物乳液型消泡剂样品A-样品E在造纸黑液测试中具有优异的消泡抑制泡的效果，前期泡沫下降速率快，后期泡沫上升速度慢，样品F-样品I前期消泡速度较慢，同时后期泡沫回升速度快。

Claims (6)

  1. 一种聚合物乳液型消泡剂及其制备方法，其特征在于，所述的聚合物乳液消泡剂由以下组分组成：活性物占消泡剂总质量的10-35％，填料粒子占消泡剂总质量的3-8％，水占消泡剂总质量的60-85％，增稠剂占消泡剂总质量的0.5-3％；
    一种聚合物乳液型消泡剂及其制备方法，所述活性物由丙烯酸酯，烯丙基聚醚，催化剂组成，其中丙烯酸酯占活性物总质量的29-70％，烯丙基聚醚占活性物总质量的29-70％，催化剂占活性物总质量的0.5-2％；
    一种聚合物乳液型消泡剂及其制备方法，制备步骤如下：
    (1)活性物的制备：将丙烯酸酯，催化剂加入烧瓶中，搅拌时间30-90min，将上述混合物滴入含有烯丙基聚醚的反应器中，反应温度60-100℃，滴加反应时间为2-8h；
    (2)将活性物，填料粒子，增稠剂置于高速搅拌器中，搅拌速度为1500-2500rpm，缓慢滴入水，搅拌时间30-120min后，得到聚合物乳液消泡剂。
  2. 如权利要求1所述的一种聚合物乳液型消泡剂及其制备方法，其特征在于所述丙烯酸酯选自丙烯酸羟乙酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸十八酯、丙烯酸异辛酯中的一种或两种以上任意比例混合。
  3. 如权利要求1所述的一种聚合物乳液型消泡剂及其制备方法，其特征在于，所述填料粒子选自疏水白炭黑、二氧化钛、氧化镁、氧化 铝、乙二胺双硬脂酸酰胺(EBS)、硬脂酸铝中的一种或几种。
  4. 如权利要求3所述的一种聚合物乳液型消泡剂及其制备方法，其特征在于所述填料粒子比表面积为150～500m 2/g。
  5. 如权利要求1所述的一种聚合物乳液型消泡剂及其制备方法，其特征在于，所述增稠剂为聚丙烯酰胺、卡波姆、汉生胶、聚丙烯酸酯、甲基纤维素、羧甲基纤维素、羟乙基纤维素、乙基纤维素中一种或几种。
  6. 如权利要求1所述的一种聚合物乳液型消泡剂及其制备方法，其特征在于，所述烯丙基聚醚A的结构通式如下：CH 2＝CHCH 2(OCH 2CH 2) a(OCH 2CHCH 3) b其中a为1-10整数，b为10-100整数。
PCT/CN2020/081539 2020-03-23 2020-03-27 一种聚合物乳液型消泡剂及其制备方法 WO2021189393A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010207349.8A CN111484630A (zh) 2020-03-23 2020-03-23 一种聚合物乳液型消泡剂及其制备方法
CN202010207349.8 2020-03-23

Publications (1)

Publication Number Publication Date
WO2021189393A1 true WO2021189393A1 (zh) 2021-09-30

Family

ID=71812368

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/081539 WO2021189393A1 (zh) 2020-03-23 2020-03-27 一种聚合物乳液型消泡剂及其制备方法

Country Status (2)

Country Link
CN (1) CN111484630A (zh)
WO (1) WO2021189393A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116289309A (zh) * 2023-02-02 2023-06-23 江苏斯德瑞克化工有限公司 一种环保型抄纸聚醚消泡剂的加工方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102428142A (zh) * 2009-05-15 2012-04-25 詹姆斯·马丁 聚合消泡添加剂
CN102649021A (zh) * 2012-05-03 2012-08-29 安微銮威化工科技开发有限公司 一种非硅复合乳液型消泡剂及其制备方法
CN102762620A (zh) * 2010-02-26 2012-10-31 科莱恩金融(Bvi)有限公司 聚合物及其作为具有抑泡作用的分散剂的用途
US20140221508A1 (en) * 2011-10-24 2014-08-07 San Nopco Ltd. Defoaming agent
CN107847821A (zh) * 2015-08-19 2018-03-27 Jxtg能源株式会社 消泡剂和润滑油组合物
CN108786188A (zh) * 2017-05-05 2018-11-13 江苏四新科技应用研究所股份有限公司 一种非硅消泡剂
CN110508037A (zh) * 2019-08-29 2019-11-29 安徽銮威化工科技开发有限公司 一种非硅消泡剂及其制备装置
CN111013201A (zh) * 2019-12-03 2020-04-17 江苏四新科技应用研究所股份有限公司 消泡剂组合物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106459585B (zh) * 2014-04-03 2021-05-28 道康宁东丽公司 新型硅酮表面活性剂、w/o乳液组合物、粉末组合物及其美容/医药应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102428142A (zh) * 2009-05-15 2012-04-25 詹姆斯·马丁 聚合消泡添加剂
CN102762620A (zh) * 2010-02-26 2012-10-31 科莱恩金融(Bvi)有限公司 聚合物及其作为具有抑泡作用的分散剂的用途
US20140221508A1 (en) * 2011-10-24 2014-08-07 San Nopco Ltd. Defoaming agent
CN102649021A (zh) * 2012-05-03 2012-08-29 安微銮威化工科技开发有限公司 一种非硅复合乳液型消泡剂及其制备方法
CN107847821A (zh) * 2015-08-19 2018-03-27 Jxtg能源株式会社 消泡剂和润滑油组合物
CN108786188A (zh) * 2017-05-05 2018-11-13 江苏四新科技应用研究所股份有限公司 一种非硅消泡剂
CN110508037A (zh) * 2019-08-29 2019-11-29 安徽銮威化工科技开发有限公司 一种非硅消泡剂及其制备装置
CN111013201A (zh) * 2019-12-03 2020-04-17 江苏四新科技应用研究所股份有限公司 消泡剂组合物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116289309A (zh) * 2023-02-02 2023-06-23 江苏斯德瑞克化工有限公司 一种环保型抄纸聚醚消泡剂的加工方法

Also Published As

Publication number Publication date
CN111484630A (zh) 2020-08-04

Similar Documents

Publication Publication Date Title
CA2758575C (en) Polymeric defoamer additive
CN110283322B (zh) 一种有机硅组合物
CN105498305B (zh) 一种有机硅消泡组合物
CA1299056C (en) Silicone antifoams
EP0802230B1 (en) Dispersible silicone compostions
CN103669108B (zh) 一种造纸工业用有机硅消泡剂及其制备方法
CN111013201A (zh) 消泡剂组合物
CN110483701A (zh) 一种水溶性超支化稠油降粘驱油剂及其制备方法
CN109180959B (zh) 一种提高有机硅乳液稳定性的方法
CN109316782B (zh) 一种改性聚硅氧烷组合物的制备及应用
CN114191854B (zh) 一种聚醚改性有机硅氧烷乳液型消泡剂及其制备方法
WO2021189393A1 (zh) 一种聚合物乳液型消泡剂及其制备方法
CN108299938B (zh) 一种涂料和油墨的消泡剂及其制备方法
US4764574A (en) Inverse emulsion polymerization with sorbitan fatty acid esters and ethoxylated alcohol
CN102432741B (zh) 一种焦化油水分离剂及其制备方法和使用方法
US5055229A (en) Silicone antifoams
CN102242523B (zh) 一种低温抄纸体系用消泡剂
JPS6157210A (ja) 石油からのガスの分離方法
RU2278873C2 (ru) Дисперсии полимеров типа "вода в масле" с повышенной экологической безопасностью
CA2111219A1 (en) An electroviscous fluid based on polyether acrylates as disperse phase
CN114146455B (zh) 消泡组合物
CN1113912C (zh) 羧酸和多烯不饱和羧酸衍生物的共聚物及其作为增稠剂或分散剂的使用
CN113577835A (zh) 一种有机硅组合物
CN109233296A (zh) 一种提高有机硅乳液稳定性的方法
CN114316610A (zh) 一种有机硅乳液的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20927102

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20927102

Country of ref document: EP

Kind code of ref document: A1