WO2023040044A1 - 一种聚合物型消泡剂及制备方法 - Google Patents
一种聚合物型消泡剂及制备方法 Download PDFInfo
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- WO2023040044A1 WO2023040044A1 PCT/CN2021/132744 CN2021132744W WO2023040044A1 WO 2023040044 A1 WO2023040044 A1 WO 2023040044A1 CN 2021132744 W CN2021132744 W CN 2021132744W WO 2023040044 A1 WO2023040044 A1 WO 2023040044A1
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- acid
- oil
- polymer
- defoamer
- preparation
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- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 239000013530 defoamer Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000344 soap Substances 0.000 claims abstract description 10
- 239000002199 base oil Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000194 fatty acid Substances 0.000 claims description 22
- 229920000570 polyether Polymers 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 16
- 101150065749 Churc1 gene Proteins 0.000 claims description 16
- 102100038239 Protein Churchill Human genes 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 claims description 6
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 6
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000011973 solid acid Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 3
- 235000019774 Rice Bran oil Nutrition 0.000 claims description 3
- 235000019485 Safflower oil Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000003240 coconut oil Substances 0.000 claims description 3
- 235000019864 coconut oil Nutrition 0.000 claims description 3
- 235000005687 corn oil Nutrition 0.000 claims description 3
- 239000002285 corn oil Substances 0.000 claims description 3
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 239000002385 cottonseed oil Substances 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 125000002950 monocyclic group Chemical group 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000004006 olive oil Substances 0.000 claims description 3
- 235000008390 olive oil Nutrition 0.000 claims description 3
- 239000003346 palm kernel oil Substances 0.000 claims description 3
- 235000019865 palm kernel oil Nutrition 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- 239000008165 rice bran oil Substances 0.000 claims description 3
- 235000005713 safflower oil Nutrition 0.000 claims description 3
- 239000003813 safflower oil Substances 0.000 claims description 3
- 239000008159 sesame oil Substances 0.000 claims description 3
- 235000011803 sesame oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000855 fermentation Methods 0.000 abstract 1
- 230000004151 fermentation Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- -1 siloxanes Chemical class 0.000 description 7
- 230000003254 anti-foaming effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007957 coemulsifier Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D19/0413—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-atoms
Definitions
- the invention belongs to the field of fine chemicals, and in particular relates to a polymer type defoamer and a preparation method.
- Defoamer is a fine chemical additive whose main function is to suppress and eliminate many harmful foams produced during industrial production.
- silicone-based defoamers have the characteristics of rapid defoaming, long antifoaming time, safety and non-toxicity due to their low surface tension, but they are difficult to dissolve in water, and siloxanes are prone to occur in strong alkaline environment systems. Reactive, and prone to shrinkage and oil spots.
- silicone polymer defoamer Rather than silicone polymer defoamer, it has excellent foam suppression, defoaming, and defoaming effects, and it is extremely fast, and its extremely low shrinkage tendency is especially suitable for systems that are prone to shrinkage.
- CN201110203178.2 A preparation method of a non-silicon defoamer, using white mineral oil, white carbon black, polyether, dimethyl silicone oil, fatty acid amide, thickener EBS, tributyl phosphate emulsifier and co-emulsifier after mixing Fully emulsified, this type of defoamer is non-toxic, easy to use, good in dispersibility, thermal stability and chemical stability, and has excellent defoaming performance and stable foam suppression performance.
- CN201010126614.6 A production method of fatty acid amide defoamer for papermaking.
- the finished product is obtained by uniformly dispersing surfactant fatty acid amide and glycol monoester in mineral oil system, and supplemented with inorganic active groups such as modified silicon dioxide. points, improve the defoaming and antifoaming efficiency of the defoamer.
- CN201810578923.3 A non-silicon defoamer and its preparation method, which proposes hydrogenated castor oil, through a special process, while ensuring the defoaming and antifoaming performance, the product stability is guaranteed; on the other hand, through a special process, the secondary Introduce hydrogenated castor oil substances, and use the "returning coarse” characteristics of hydrogenated castor oil substances to further improve the anti-foaming performance of the product; and in order to make the "returning coarse” hydrogenated castor oil substances have good compatibility with the use system
- the introduction of castor oil polyoxyethylene polyoxypropylene ether oleate with a special structure ensures good compatibility of the product.
- the above patents all adopt the traditional emulsifier technology and have not yet designed the polymer from the molecular structure. In the application of defoamers, there may be problems of difficult emulsification or emulsion layering, and instability.
- the invention mainly solves the problem that the current polymer is used as an active substance to prepare the defoamer, which cannot be effectively emulsified or has poor stability after emulsification, and proposes a way to prepare the defoamer by constructing a hydrophilic segment in the molecular structure of the polymer , fundamentally solve the existing technical problems.
- a method for preparing a polymer defoamer is composed of the following components in mass proportion: polymer 12-35%, silicon dioxide 2-8%, metal soap 3-10% , carrier oil 48-82%, the sum of the above raw materials is 100%;
- the polymer is composed of the following raw materials according to the mass ratio: 21-51% of dicarboxylic acid, 47-78% of amino polyether compound, 0.2-2.3% of catalyst, and the sum of the above raw materials is 100%;
- the dicarboxylic acid is selected from sebacic acid, azelaic acid, adipic acid, nylon acid, 1,4-cyclohexanedicarboxylic acid, octadecanedioic acid, hexadecanedioic acid, eicosanedioic acid, One of docosanedioic acid and C21 monocyclic dicarboxylic acid;
- the general formula of the amino polyether compound is CH 3 -(OCH 2 CH(R 1 )) X -(OCH 2 CHCH 3 ) Y -NH 2 ; where R 1 is H or CH 3 , and x is 1-50 Integer, y is an integer of 1-50;
- the catalyst is nitric acid, sulfuric acid, phosphoric acid, and one or more of solid acids are mixed in any proportion;
- the silica is fumed hydrophobic silica with a specific surface area of 20-500m 2 /g;
- the metal soap is one or more of magnesium salts, aluminum salts, calcium salts, and zinc salts of fatty acids; preferably aluminum fatty acids, specifically selected from one or more of mono-fatty acid aluminum, di-fatty acid aluminum, and tri-fatty acid aluminum species, mixed in any proportion;
- the carrier oil is selected from white oil, soybean oil, palm kernel oil, cottonseed oil, rapeseed oil, coconut oil, corn oil, sesame oil, rice bran oil, castor oil, olive oil, linseed oil, safflower oil, peanut oil or more, mixed in any proportion.
- a kind of polymer type defoamer and preparation method it is characterized in that preparation method comprises the following steps:
- Amino polyethers of different structures are introduced into the molecular structure of the polymer. Since the polyether has excellent anti-foaming performance and good compatibility in mineral oil, the breadth of its application in the formulation design of the defoamer is enhanced.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
一种聚合物消泡剂及制备方法,主要由以下原料按重量配比组成:聚合物12-35%,二氧化硅2-8%,金属皂3-10%,载体油40-85%,其中聚合物为主要活性物质。所述聚合物消泡剂的制备方法工艺简单,成本低廉,性能优异,可广泛应用于造纸制浆,涂料,油墨,粘结剂,发酵等行业。
Description
本发明属精细化工领域,尤其涉及一种聚合物型消泡剂及制备方法。
消泡剂是一种精细化学品添加剂,其主要功能是抑制和消除工业生产过程中产生的许多有害泡沫。目前,有机硅类消泡剂由于其较低的表面张力,具有消泡迅速、抑泡时间长和安全无毒等特点,但它难溶于水,在强碱环境体系中易发生硅氧烷反应,且容易缩孔,容易起油斑。而非硅聚合物消泡剂,极优异的抑泡、脱泡、消泡效果,且极为迅速,极低的缩孔倾向特别适合于极易缩孔的体系。
CN201110203178.2一种非硅消泡剂的制备方法,采用白矿油、白炭黑、聚醚、二甲基硅油、脂肪酸酰胺、增稠剂EBS、磷酸三丁酯乳化剂助乳化剂混合后充分乳化,此类消泡剂无毒、使用方便、分散性、热稳定和化学稳定性好,具有优良的消泡性能和稳定的抑泡性能。CN201010126614.6一种造纸用脂肪酸酰胺消泡剂的生产方法,将表面活性剂脂肪酸酰胺和二元醇单酯均匀分散于矿物油体系中即为成品,辅以改性二氧化硅等无机活性组分,提高消泡剂的消泡抑泡效率。CN201810578923.3一种非硅消泡剂及其制备方法,提出氢化蓖麻油类物质,通过特殊工艺,保证消抑泡性能的同时,产品稳定性得到保证;另一方面,通过特殊工艺,二次引入氢化蓖麻油类物质,利用氢 化蓖麻油类物质的“返粗”特性,进一步提高了产品的消抑泡性能;而且为了使得“返粗”氢化蓖麻油类物质与使用体系具有良好的相容性,引入特殊结构的蓖麻油聚氧乙烯聚氧丙烯醚油酸酯,保证产品具有良好的相容性。以上专利均采用传统乳化剂工艺及尚未从分子结构中进行聚合物的设计,在消泡剂应用中可能存在难乳化或乳液分层,不稳定的问题。
发明内容
本发明主要解决目前应用聚合物作为活性物制备消泡剂,无法进行有效乳化或乳化后存在稳定性差的问题,提出了一种聚合物分子结构中构建亲水性链段的方式制备消泡剂,从根本上解决现有技术难题。
本发明的技术方案如下:
一种聚合物型消泡剂制备方法,所述的聚合物消泡剂由以下组分按质量配比组成:聚合物12-35%,二氧化硅2-8%,金属皂3-10%,载体油48-82%,以上原料之和为100%;
A聚合物
所述聚合物由以下原料按质量配比组成:二元羧酸21-51%,胺基聚醚化合物47-78%,催化剂0.2-2.3%,以上原料之和为100%;
所述二元羧酸选自癸二酸、壬二酸、己二酸、尼龙酸,1,4-环己二甲酸,十八烷二酸、十六烷二酸、二十烷二酸、二十二烷二酸、C21单环二元羧酸中的一种;
所述胺基聚醚化合物通式为CH
3-(OCH
2CH(R
1))
X-(OCH
2CHCH
3)
Y-NH
2;其中R
1为H或CH
3,x为1-50的整数,y为1-50的整数;
所述催化剂为硝酸、硫酸,磷酸,固体酸中一种或多种按任意比例混合;
B二氧化硅
所述二氧化硅为比表面积为20~500m
2/g的气相法疏水二氧化硅;
C金属皂
所述金属皂为脂肪酸的镁盐、铝盐、钙盐、锌盐中的一种或多种;优选脂肪酸铝,具体选自单脂肪酸铝、双脂肪酸铝、三脂肪酸铝中的一种或多种,按任意比例混合;
D载体油
所述载体油选自白油、大豆油、棕榈仁油、棉籽油、菜籽油、椰子油、玉米油、芝麻油、米糠油、蓖麻油、橄榄油、亚麻油、红花油、花生油中一种或多种,按任意比例混合。
一种聚合物型消泡剂及制备方法,其特征在于制备方法包括以下步骤:
(1)分别将二元羧酸和催化剂按照规定量加入反应釜中,开启搅拌器,升高温度60-250℃,缓慢滴加规定量的胺基聚醚化合物,滴加反应时间为2-8h,反应结束后获得聚合物。
(2)按照规定量依次将聚合物、二氧化硅、金属皂及载体油置于反应釜中,升高温度40-220℃,转速100-3000rpm,高速分散0.5-2h, 反应完成后降温至室温获得聚合物型消泡剂。
本发明优势在于:
1、通过引入胺基聚醚与二元羧酸发生酰胺反应,利用二元酸羧基与胺聚醚中胺基进行脱水缩合反应形成酰胺聚合物,同时由于分子结构中含有聚醚链段可以有效调节聚合物的亲水性能,从而解决了聚合物在制备消泡剂配方中不易乳化问题。
2、采用不同结构的胺基聚醚引入聚合物分子结构中,由于聚醚具有优异抑制泡沫的性能和在矿物油中良好的相融性能,增强了其应用于消泡剂配方设计的宽度。
3、解决了采用传统方法(司盘,吐温,聚氧乙烯醚等乳化剂)乳化聚合物后出现各种不稳定问题(如:乳液稳定性差,在应用耐酸碱环境中易破乳,失去消泡性能)。
4、利用酰胺聚合物自身结构中酰胺键相比传统有机硅消泡剂硅氧硅键,使其具有良好的耐碱性能,拓展在苛刻的环境中具有良好的消泡性能。
实施例1.
(1)将210g癸二酸和18g磷酸置于反应釜中,开启搅拌器,升温至120℃,向反应釜中缓慢滴加772g胺基聚醚化合物CH
3-(OCH
2CH
2)-(OCH
2CHCH
3)
8-NH
2,反应时间为3.5h后获得聚合物;
(2)取上述反应后聚合物130g,加入20g比表面积为200m
2/g的气相 法疏水二氧化硅,30g单脂肪酸铝,白油820g置于反应釜中,升高温度100℃,转速600rpm,高速分散0.5h,反应完成后降温至室温后获得聚合物型消泡剂M1.其消泡性能见表1.
实施例2.
(1)将480g尼龙酸和21g硫酸置于反应釜中,开启搅拌器,升温至132℃,向反应釜中缓慢滴加499g胺基聚醚化合物CH
3-(OCH
2CH
2)
17-(OCH
2CHCH
3)-NH
2,反应时间为4.5h后获得聚合物;
(2)取上述反应后聚合物180g,加入35g比表面积为280m
2/g的气相法疏水二氧化硅,45g双脂肪酸铝,大豆油440g,玉米油300g置于反应釜中,升高温度120℃,转速900rpm,高速分1.2h,反应完成后降温至室温后获得聚合物型消泡剂M2.其消泡性能见表1.
实施例3.
(1)将260g己二酸和7g磷酸置于反应釜中,开启搅拌器,升温至145℃,向反应釜中缓慢滴加733g胺基聚醚化合物CH
3-(OCH
2CH
2)
28-(OCH
2CHCH
3)
12-NH
2,反应时间为7.5h后获得聚合物;
(2)取上述反应后聚合物220g,加入75g比表面积为320m
2/g的气相法疏水二氧化硅,75g脂肪酸镁,菜籽油630g置于反应釜中,升高温度200℃,转速1100rpm,高速分散2h,反应完成后降温至室温后获得聚合物型消泡剂M3.其消泡性能见表1.
实施例4.
(1)将211g十八烷二酸和9g固体酸置于反应釜中,开启搅拌器,升温至185℃,向反应釜中缓慢滴加780g胺基聚醚化合物CH
3- (OCH
2CH
2)
50-(OCH
2CHCH
3)
28-NH
2,反应时间为6.5h后获得聚合物;
(2)取上述反应后聚合物348g,加入77g比表面积为420m
2/g的气相法疏水二氧化硅,95g三脂肪酸铝,200g棕榈仁油和280g棉籽油,置于反应釜中,升高温度148℃,转速1400rpm,高速分散1.7h,反应完成后降温至室温后获得聚合物型消泡剂M4.其消泡性能见表1.
实施例5.
(1)将310gC21单环二元羧酸和2g硝酸置于反应釜中,开启搅拌器,升温至195℃,向反应釜中缓慢滴加688g胺基聚醚化合物CH
3-(OCH
2CH
2)
35-(OCH
2CHCH
3)
46-NH
2,反应时间为4.5h后获得聚合物;
(2)取上述反应后聚合物350g,加入55g比表面积为500m
2/g的气相法疏水二氧化硅,30g单脂肪酸铝,,30g双脂肪酸铝,花生油535g置于反应釜中,升高温度60℃,转速1500rpm,高速分散1.6h,反应完成后降温至室温后获得聚合物型消泡剂M5.其消泡性能见表1.
实施例6.
(1)将360g十六烷二酸、10g硝酸和13g硫酸置于反应釜中,开启搅拌器,升温至60℃,向反应釜中缓慢滴加617g胺基聚醚化合物CH
3-(OCH
2CHCH
3)
40-(OCH
2CHCH
3)
18-NH
2,反应时间为8h后获得聚合物;
(2)取上述反应后聚合物234g,加入80g比表面积为50m
2/g的气相法疏水二氧化硅,100g脂肪酸钙,蓖麻油586g置于反应釜中,升高温度40℃,转速2500rpm,高速分散2h,反应完成后降温至室温后获得聚合物型消泡剂M6.其消泡性能见表1.
实施例7.
(1)将400g二十烷二酸、5g固体酸、5g硫酸以及5g磷酸置于反应釜中,开启搅拌器,升温至250℃,向反应釜中缓慢滴加585g胺基聚醚化合物CH
3-(OCH
2CHCH
3)
8-(OCH
2CHCH
3)
25-NH
2,反应时间为2.5h后获得聚合物;
(2)取上述反应后聚合物158g,加入65g比表面积为150m
2/g的气相法疏水二氧化硅,20g双脂肪酸铝和65g三脂肪酸铝,392g椰子油和300g米糠油置于反应釜中,升高温度220℃,转速3000rpm,高速分散1h,反应完成后降温至室温后获得聚合物型消泡剂M7.其消泡性能见表1.
实施例8.
(1)将510g壬二酸、10g硫酸和10g磷酸置于反应釜中,开启搅拌器,升温至80℃,向反应釜中缓慢滴加470g胺基聚醚化合物CH
3-(OCH
2CHCH
3)
10-(OCH
2CHCH
3)
35-NH
2,反应时间为4h后获得聚合物;
(2)取上述反应后聚合物120g,加入50g比表面积为500m
2/g的气相二氧化硅,20g三脂肪酸铝、20g单脂肪酸铝和10g脂肪酸锌,700g芝麻油和80g亚麻油置于反应釜中,升高温度180℃,转速2000rpm,高速分散0.5h,反应完成后降温至室温后获得聚合物型消泡剂M8.其消泡性能见表1.
实施例9.
(1)将450g1,4-环己二甲酸1g磷酸、2g硝酸、2g硫酸、1g固体酸置于反应釜中,开启搅拌器,升温至100℃,向反应釜中缓慢滴加544g 胺基聚醚化合物CH
3-(OCH
2CHCH
3)
25-(OCH
2CHCH
3)
40-NH
2,反应时间为5h后获得聚合物;
(2)取上述反应后聚合物330g,加入60g比表面积为100m
2/g的气相法疏水二氧化硅,80g脂肪酸锌,橄榄油530g置于反应釜中,升高温度80℃,转速300rpm,高速分散1.8h,反应完成后降温至室温后获得聚合物型消泡剂M9.其消泡性能见表1.
实施例10.
(1)将510g二十二烷二酸和4g硫酸置于反应釜中,开启搅拌器,升温至220℃,向反应釜中缓慢滴加486g胺基聚醚化合物CH
3-(OCH
2CH
2)
20-(OCH
2CHCH
3)
50-NH
2,反应时间为2h后获得聚合物;
(2)取上述反应后聚合物230g,加入50g比表面积为20m
2/g的气相法疏水二氧化硅,20g双脂肪酸铝和50g脂肪酸钙,红花油650g置于反应釜中,升高温度160℃,转速100rpm,高速分1.5h,反应完成后降温至室温后获得聚合物型消泡剂M10.其消泡性能见表1.
对比例1
市售有机硅乳液消泡剂M11;
对比例2
市售脂肪醇乳液消泡剂M12;
对比例3
市售聚醚消泡剂M13;
表1.消泡剂性能对比
从上述数据可以明显看出:本发明消泡剂M1-M10均优于市售对比样品。
Claims (5)
- 一种聚合物型消泡剂制备方法,其特征在于,所述的聚合物消泡剂由以下组分按质量配比组成:聚合物12-35%,二氧化硅2-8%,金属皂3-10%,载体油48-82%;A聚合物,所述聚合物由以下原料按质量配比组成:二元羧酸21-51%,胺基聚醚化合物47-78%,催化剂0.2-2.3%;B二氧化硅,所述二氧化硅为比表面积为20~500m 2/g的气相法疏水二氧化硅;C金属皂,所述金属皂为脂肪酸的镁盐、铝盐、钙盐、锌盐中的一种或多种,按照任意比例混合;D载体油,所述载体油选自白油、大豆油、棕榈仁油、棉籽油、菜籽油、椰子油、玉米油、芝麻油、米糠油、蓖麻油、橄榄油、亚麻油、红花油、花生油中一种或多种,按任意比例混合;一种聚合物型消泡剂制备方法为:(1)分别将二元羧酸和催化剂按照规定量加入反应釜中,开启搅拌器,升高温度60-250℃,缓慢滴加规定量的胺基聚醚化合物,滴加反应时间为2-8h,反应结束后获得聚合物。(2)按照规定量依次将聚合物、二氧化硅、金属皂及载体油置于反应釜中,升高温度40-220℃,转速100-3000rpm,高速分散0.5-2h,反应完成后降温至室温获得聚合物型消泡剂。
- 如权利要求1所述的一种聚合物型消泡剂及制备方法,其特征在于所述的二元羧酸选自癸二酸、壬二酸、己二酸、尼龙酸,1,4-环己 二甲酸,十八烷二酸、十六烷二酸、二十烷二酸、二十二烷二酸、C21单环二元羧酸中的一种。
- 如权利要求1所述的一种聚合物型消泡剂制备方法,其特征在于所述的胺基聚醚化合物,通式如下:CH 3—(OCH 2CH(R 1)) X-(OCH 2CHCH 3) Y-NH 2其中R 1为H或CH 3,x为1-50的整数,y为0-50的整数。
- 如权利要求1所述的一种聚合物型消泡剂制备方法,其特征在于所述的催化剂选自硝酸、硫酸,磷酸,固体酸中一种或多种按任意比例混合。
- 如权利要求1所述的一种聚合物型消泡剂制备方法,其特征在于金属皂选自脂肪酸铝,具体选自单脂肪酸铝、双脂肪酸铝、三脂肪酸铝中的一种或多种按任意比例混合。
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