CN110511315A - A kind of high-barrier vinylidene chloride-acrylate emulsion and preparation method thereof - Google Patents
A kind of high-barrier vinylidene chloride-acrylate emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN110511315A CN110511315A CN201910857451.XA CN201910857451A CN110511315A CN 110511315 A CN110511315 A CN 110511315A CN 201910857451 A CN201910857451 A CN 201910857451A CN 110511315 A CN110511315 A CN 110511315A
- Authority
- CN
- China
- Prior art keywords
- vinylidene chloride
- acrylate
- acrylate emulsion
- emulsion
- emulsion according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 54
- STWZWUFRTQEEMW-UHFFFAOYSA-N 1,1-dichloroethene;prop-2-enoic acid Chemical compound ClC(Cl)=C.OC(=O)C=C STWZWUFRTQEEMW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004945 emulsification Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 17
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000006174 pH buffer Substances 0.000 claims abstract description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 11
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000006179 pH buffering agent Substances 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 abstract description 12
- -1 acrylic ester Chemical class 0.000 abstract description 3
- 239000006210 lotion Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 9
- 239000005033 polyvinylidene chloride Substances 0.000 description 9
- 239000005022 packaging material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
技术领域technical field
本发明属于涂料领域，具体涉及一种高阻隔性偏氯乙烯-丙烯酸酯乳液及其制备方法。The invention belongs to the field of coatings, and in particular relates to a high-barrier vinylidene chloride-acrylate emulsion and a preparation method thereof.
背景技术Background technique
聚偏氯乙烯(简称PVDC)是目前广泛应用于食品、医药等重要阻隔包装材料之一。近年来，基于偏氯乙烯单体合成的乳液不含易燃和有毒性的溶剂，而且涂膜具有良好的隔氧防水性能，它能使包装物免受环境中氧气、水蒸气、众多酸碱和化学药品的腐蚀。除此之外，使用PVDC制作的膜材料还有很强的韧性、高低温耐受性以及热封印刷性等性能，近60年来PVDC包装材料已大规模地应用在食品、军用品、药品、医药品等的包装，PVDC在现代高阻隔包装领域中也受到越来越多的重视。与此同时，PVDC材料还被业界虑为“绿色”包装材料，因为相比使用市面普通包装材料如聚乙烯、铝膜等，PVDC包装膜的材料用量将大幅减少，这能减少资源的浪费以及废弃物的产生，最终达到资源利用和环境保护双赢的目的。但由于其热稳定性较差，导致其存在难以加工的缺陷，而引入丙烯酸酯作为共聚单体，可以从反应内部增加平稳，则可以明显地增强树脂的稳定性、阻隔性能，赋予了乳液更加优异的性能。Polyvinylidene chloride (PVDC for short) is one of the important barrier packaging materials widely used in food, medicine and so on. In recent years, the emulsion synthesized based on vinylidene chloride monomer does not contain flammable and toxic solvents, and the coating film has good oxygen barrier and waterproof performance, which can protect the packaging from oxygen, water vapor, and many acids and bases in the environment. and chemical corrosion. In addition, the film materials made of PVDC have strong toughness, high and low temperature resistance, and heat-sealing printability. In the past 60 years, PVDC packaging materials have been widely used in food, military supplies, pharmaceuticals, For the packaging of pharmaceuticals, PVDC has also received more and more attention in the field of modern high-barrier packaging. At the same time, PVDC materials are also considered as "green" packaging materials by the industry, because compared with common packaging materials such as polyethylene and aluminum films on the market, the amount of PVDC packaging film materials will be greatly reduced, which can reduce the waste of resources and The generation of waste ultimately achieves the win-win goal of resource utilization and environmental protection. However, due to its poor thermal stability, it has the defect that it is difficult to process, and the introduction of acrylate as a comonomer can increase the stability from the inside of the reaction, which can significantly enhance the stability and barrier properties of the resin, giving the emulsion more Excellent performance.
CN104114585A公开了一种用于泡罩包装用膜的偏二氯乙烯系共聚物乳液，不足之处是抗冲击强度较低、合成工艺较复杂，不利于生产。CN102876149A公开了一种涂布用自粘性聚偏二氯乙烯乳液及其制备方法，不足之处是热稳定性和抗黄变能力较差，从而导致阻隔性能降低。CN104114585A discloses a vinylidene chloride-based copolymer emulsion used for blister packaging films. The disadvantages are low impact strength and complex synthesis process, which is not conducive to production. CN102876149A discloses a self-adhesive polyvinylidene chloride emulsion for coating and a preparation method thereof. The disadvantage is that the heat stability and anti-yellowing ability are poor, which leads to a decrease in barrier performance.
发明内容Contents of the invention
本发明的目的是为了解决现有的聚偏氯乙烯共聚物乳液阻隔性能差的问题，而提供一种高阻隔性偏氯乙烯-丙烯酸酯乳液及其制备方法。The object of the present invention is to solve the problem of poor barrier property of the existing polyvinylidene chloride copolymer emulsion, and provide a high barrier property vinylidene chloride-acrylate emulsion and a preparation method thereof.
为达到上述发明目的，采用如下的技术方案：In order to achieve the above-mentioned purpose of the invention, adopt following technical scheme:
本发明首先提供一种高阻隔性偏氯乙烯-丙烯酸酯乳液，按照重量份数计，包括如下组分：The present invention firstly provides a high-barrier vinylidene chloride-acrylate emulsion, which comprises the following components in parts by weight:
优选的是，所述的丙烯酸酯类单体为丙烯酸甲酯、丙烯酸丁酯、丙烯酸异辛酯或甲基丙烯酸甲酯的一种或几种。Preferably, the acrylate monomer is one or more of methyl acrylate, butyl acrylate, isooctyl acrylate or methyl methacrylate.
优选的是，所述的引发剂为过硫酸钾、过硫酸钠、过硫酸铵和亚硫酸氢钠中的一种或几种。Preferably, the initiator is one or more of potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite.
优选的是，所述的引发剂为过硫酸钾和亚硫酸氢钠按照质量比为4：1的混合物。Preferably, the initiator is a mixture of potassium persulfate and sodium bisulfite in a mass ratio of 4:1.
优选的是，所述的乳化剂为十二烷基硫酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠和OP-10中的一种或两种。Preferably, the emulsifier is one or both of sodium lauryl sulfate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate and OP-10.
优选的是，所述的乳化剂为十二烷基硫酸钠和OP-10按照质量比为3：1的混合物。Preferably, the emulsifier is a mixture of sodium lauryl sulfate and OP-10 in a mass ratio of 3:1.
优选的是，所述pH缓冲剂为碳酸钠。Preferably, the pH buffer is sodium carbonate.
本发明还提供一种高阻隔性偏氯乙烯-丙烯酸酯乳液的制备方法，包括以下步骤：The present invention also provides a method for preparing a high-barrier vinylidene chloride-acrylate emulsion, comprising the following steps:
(1)预乳化：向反应釜中加入偏氟乙烯、丙烯酸酯类单体、水、乳化剂和pH缓冲剂，得到混合乳液，开启压力釜搅拌，温度为常温，氮气吹扫1～3min，预乳化30～60min，得到预聚物；(1) Pre-emulsification: Add vinylidene fluoride, acrylate monomer, water, emulsifier and pH buffer to the reaction kettle to obtain a mixed emulsion, turn on the pressure kettle to stir, keep the temperature at room temperature, and purge with nitrogen for 1 to 3 minutes. Pre-emulsify for 30-60 minutes to obtain a prepolymer;
(2)乳液聚合：向反应釜中加入引发剂，密闭反应釜升温至55～65℃，反应4～8小时，得到偏氯乙烯-丙烯酸酯乳液。(2) Emulsion polymerization: add an initiator into the reactor, heat up the sealed reactor to 55-65° C., and react for 4-8 hours to obtain a vinylidene chloride-acrylate emulsion.
优选的是，所述步骤(1)中搅拌速率为140～160r/min。Preferably, the stirring rate in the step (1) is 140-160 r/min.
优选的是，所述的步骤⑴中混合乳液的固含量为40～50％。Preferably, the solid content of the mixed emulsion in the step (1) is 40-50%.
本发明的有益效果Beneficial effects of the present invention
本发明提供一种偏氯乙烯-丙烯酸酯乳液，该偏氯乙烯-丙烯酸酯乳液由于丙烯酸酯的引入，通过合理控制丙烯酸酯单体的使用量，采用合适的乳化剂做预乳化，并控制聚合过程中乳化剂、引发剂、pH调节剂的比例和工艺条件，使得到的偏氯乙烯-丙烯酸酯乳液具有良好的阻隔性能，同时也改善了乳液的综合性能，本发明还提供一种偏氯乙烯-丙烯酸酯乳液的制备方法，该制备方法简单，没有有机溶剂的加入，绿色环保。The invention provides a vinylidene chloride-acrylate emulsion. Due to the introduction of acrylate, the vinylidene chloride-acrylate emulsion can be pre-emulsified with a suitable emulsifier by rationally controlling the amount of acrylate monomer used, and controlled polymerization The ratio of emulsifier, initiator, pH regulator and process conditions in the process make the obtained vinylidene chloride-acrylate emulsion have good barrier properties, and also improve the overall performance of the emulsion. The invention also provides a vinylidene chloride The preparation method of the ethylene-acrylate emulsion is simple, does not add an organic solvent, and is environmentally friendly.
具体实施方式Detailed ways
下面结合实施例，对本发明进一步说明，下述实施例是说明性的，不是限定性的，不能以下述实施例来限定本发明的保护范围。Below in conjunction with the examples, the present invention is further described, the following examples are illustrative, not limiting, and the protection scope of the present invention cannot be limited by the following examples.
本发明首先提供一种偏氯乙烯-丙烯酸酯乳液，按重量份数计，包括：The present invention firstly provides a kind of vinylidene chloride-acrylate emulsion, by weight parts, comprising:
偏氯乙烯88～92份，丙烯酸酯类单体8～12份，引发剂1～1.5份，乳化剂2.5～3.5份，pH缓冲剂0.3～0.5份。88-92 parts of vinylidene chloride, 8-12 parts of acrylate monomer, 1-1.5 parts of initiator, 2.5-3.5 parts of emulsifier, and 0.3-0.5 parts of pH buffering agent.
本发明所述的丙烯酸酯类单体优选自丙烯酸甲酯、丙烯酸丁酯、丙烯酸异辛酯和甲基丙烯酸甲酯的一种或几种，丙烯酸酯类单体的总加入量为单体总量的8～12％，优选为10％，The acrylate monomers described in the present invention are preferably selected from one or more of methyl acrylate, butyl acrylate, isooctyl acrylate and methyl methacrylate, and the total amount of acrylate monomers added is the total amount of monomers. 8-12% of the amount, preferably 10%,
本发明所述的引发剂优选为过硫酸钾、过硫酸钠、过硫酸铵和亚硫酸氢钠中的一种或几种，更优选为过硫酸钾和亚硫酸氢钠按照质量比为4：1的混合物。Initiator of the present invention is preferably one or more in potassium persulfate, sodium persulfate, ammonium persulfate and sodium bisulfite, more preferably potassium persulfate and sodium bisulfite are 4 according to the mass ratio: 1 mixture.
本发明所述的乳化剂优选为十二烷基硫酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠和OP-10中的一种或两种，更优选为十二烷基硫酸钠和OP-10按照质量比为3：1的混合物。The emulsifier of the present invention is preferably one or both of sodium lauryl sulfate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate and OP-10, more preferably dodecyl A mixture of sodium base sulfate and OP-10 in a mass ratio of 3:1.
本发明所述pH缓冲剂优选为碳酸钠。The pH buffering agent of the present invention is preferably sodium carbonate.
本发明还提供一种偏氯乙烯-丙烯酸酯乳液的制备方法，包括如下：The present invention also provides a kind of preparation method of vinylidene chloride-acrylate emulsion, comprising as follows:
(1)预乳化：向反应釜中加入偏氟乙烯、丙烯酸酯类单体、水、乳化剂、pH缓冲剂，得到混合乳液，所述的混合乳液的固含量为40～50％；开启压力釜搅拌，所述的搅拌速率优选为140～160r/min，温度为常温，氮气吹扫1～3min，预乳化30～60min，得到预聚物；(1) Pre-emulsification: add vinylidene fluoride, acrylate monomer, water, emulsifier, and pH buffering agent into the reaction kettle to obtain a mixed emulsion. The solid content of the mixed emulsion is 40% to 50%; Stir in a kettle, the stirring rate is preferably 140-160r/min, the temperature is normal temperature, nitrogen is purged for 1-3min, and pre-emulsified for 30-60min to obtain a prepolymer;
(2)乳液聚合：向反应釜中加入引发剂，密闭反应釜升温至55～65℃，反应4～8小时，得到偏氯乙烯-丙烯酸酯乳液。(2) Emulsion polymerization: add an initiator into the reactor, heat up the sealed reactor to 55-65° C., and react for 4-8 hours to obtain a vinylidene chloride-acrylate emulsion.
下面结合实例对本发明做进一步详细的描述。Below in conjunction with example the present invention is described in further detail.
实施例1Example 1
(1)预乳化：向反应釜中加入偏氯乙烯135g、丙烯酸甲酯15g、水225g、乳化剂十二烷基硫酸钠3.375g、OP-10 1.125g、pH缓冲剂碳酸钠0.6g，控制所制得乳液的固含量为40％，开启压力釜150r/min搅拌，温度为常温，氮气吹扫2min，预乳化45min。(1) Pre-emulsification: Add 135g of vinylidene chloride, 15g of methyl acrylate, 225g of water, 3.375g of emulsifier sodium lauryl sulfate, 1.125g of OP-10, 0.6g of pH buffer sodium carbonate into the reactor, and control The solid content of the prepared emulsion was 40%. The autoclave was turned on to stir at 150 r/min, the temperature was normal temperature, the nitrogen gas was purged for 2 minutes, and the pre-emulsification was carried out for 45 minutes.
(2)乳液聚合：向反应釜中加入引发剂过硫酸钾1.5g、亚硫酸氢钠0.375g，密闭反应釜升温至60℃，反应6小时，制得高阻隔性偏氯乙烯-丙烯酸酯乳液。(2) Emulsion polymerization: Add 1.5 g of initiator potassium persulfate and 0.375 g of sodium bisulfite to the reaction kettle, heat up the closed reaction kettle to 60°C, and react for 6 hours to prepare a high-barrier vinylidene chloride-acrylate emulsion .
将实施例1制备得到的偏氯乙烯-丙烯酸酯乳液进行性能测试，结果如表1所示。The vinylidene chloride-acrylate emulsion prepared in Example 1 was tested for performance, and the results are shown in Table 1.
实施例2Example 2
(1)预乳化：向反应釜中加入偏氯乙烯132g、丙烯酸丁酯18g、水180g、乳化剂十二烷基硫酸钠2.8g、OP-10 0.95g、pH缓冲剂碳酸钠0.45g，控制所制得乳液的固含量为45％，开启压力釜140r/min搅拌，温度为常温，氮气吹扫1min，预乳化30min。(1) Pre-emulsification: add vinylidene chloride 132g, butyl acrylate 18g, water 180g, emulsifier sodium lauryl sulfate 2.8g, OP-10 0.95g, pH buffer agent sodium carbonate 0.45g, control The solid content of the prepared emulsion was 45%. The autoclave was turned on to stir at 140 r/min, the temperature was normal temperature, the nitrogen gas was purged for 1 min, and the pre-emulsification was performed for 30 min.
(2)乳液聚合：向反应釜中加入引发剂过硫酸钾1.2g、亚硫酸氢钠0.3g，密闭反应釜升温至55℃，反应4小时，制得高阻隔性偏氯乙烯-丙烯酸酯乳液。(2) Emulsion polymerization: Add 1.2 g of initiator potassium persulfate and 0.3 g of sodium bisulfite to the reactor, heat up the closed reactor to 55°C, and react for 4 hours to prepare a high-barrier vinylidene chloride-acrylate emulsion .
将实施例2得到的偏氯乙烯-丙烯酸酯乳液进行性能测试，结果如表1所示。The performance test of the vinylidene chloride-acrylate emulsion obtained in Example 2 is shown in Table 1.
实施例3Example 3
(1)预乳化：向反应釜中加入偏氯乙烯138g、丙烯酸异辛酯12g、水150g、乳化剂十二烷基硫酸钠3.9375g、OP-10 1.3125g、pH缓冲剂碳酸钠0.75g，控制所制得乳液的固含量为50％，开启压力釜160r/min搅拌，温度为常温，氮气吹扫3min，预乳化60min。(1) Pre-emulsification: Add 138g of vinylidene chloride, 12g of isooctyl acrylate, 150g of water, 3.9375g of emulsifier sodium lauryl sulfate, 1.3125g of OP-10, 0.75g of pH buffer sodium carbonate into the reactor, The solid content of the prepared emulsion was controlled to 50%, the autoclave was turned on to stir at 160 r/min, the temperature was normal temperature, the nitrogen gas was purged for 3 minutes, and the pre-emulsification was carried out for 60 minutes.
(2)乳液聚合：向反应釜中加入引发剂过硫酸钾1.8g、亚硫酸氢钠0.45g，密闭反应釜升温至65℃，反应8小时，制得高阻隔性偏氯乙烯-丙烯酸酯乳液。(2) Emulsion polymerization: Add 1.8 g of initiator potassium persulfate and 0.45 g of sodium bisulfite to the reactor, heat up the closed reactor to 65°C, and react for 8 hours to prepare a high-barrier vinylidene chloride-acrylate emulsion .
将实施例3得到的偏氯乙烯-丙烯酸酯乳液进行性能测试，结果如表1所示。The performance test of the vinylidene chloride-acrylate emulsion obtained in Example 3 is shown in Table 1.
实施例4Example 4
(1)预乳化：向反应釜中加入偏氯乙烯135g、甲基丙烯酸甲酯15g、水225g、乳化剂十二烷基硫酸钠3.375g、OP-10 1.125g、pH缓冲剂碳酸钠0.6g，控制所制得乳液的固含量为40％，开启压力釜150r/min搅拌，温度为常温，氮气吹扫1min，预乳化30min。(1) Pre-emulsification: Add 135g of vinylidene chloride, 15g of methyl methacrylate, 225g of water, 3.375g of emulsifier sodium lauryl sulfate, 1.125g of OP-10, and 0.6g of pH buffer sodium carbonate into the reactor , control the solid content of the prepared emulsion to 40%, turn on the autoclave to stir at 150r/min, keep the temperature at room temperature, purging with nitrogen for 1min, and pre-emulsify for 30min.
(2)乳液聚合：向反应釜中加入引发剂过硫酸钾1.5g、亚硫酸氢钠0.375g，密闭反应釜升温至60℃，反应5小时，制得高阻隔性偏氯乙烯-丙烯酸酯乳液。(2) Emulsion polymerization: Add 1.5 g of initiator potassium persulfate and 0.375 g of sodium bisulfite into the reaction kettle, heat up the closed reaction kettle to 60°C, and react for 5 hours to prepare a high-barrier vinylidene chloride-acrylate emulsion .
将实施例4得到的偏氯乙烯-丙烯酸酯乳液进行性能测试，结果如表1所示。The performance test of the vinylidene chloride-acrylate emulsion obtained in Example 4 is shown in Table 1.
对比例1Comparative example 1
(1)预乳化：向反应釜中加入偏氯乙烯150g、水225g、乳化剂十二烷基硫酸钠3.375g、OP-10 1.125g、pH缓冲剂碳酸钠0.6g，控制所制得乳液的固含量为40％，开启压力釜150r/min搅拌，温度为常温，氮气吹扫1min，预乳化30min。(1) Pre-emulsification: add vinylidene chloride 150g, water 225g, emulsifier sodium lauryl sulfate 3.375g, OP-10 1.125g, pH buffer agent sodium carbonate 0.6g in the reactor, control the prepared emulsion The solid content is 40%, the autoclave is turned on to stir at 150r/min, the temperature is normal temperature, nitrogen is purged for 1min, and pre-emulsification is 30min.
(2)乳液聚合：向反应釜中加入引发剂过硫酸钾1.5g、亚硫酸氢钠0.375g，密闭反应釜升温至60℃，反应5小时，制得偏氯乙烯乳液。(2) Emulsion polymerization: Add 1.5 g of initiator potassium persulfate and 0.375 g of sodium bisulfite into the reactor, heat up the closed reactor to 60° C., and react for 5 hours to prepare vinylidene chloride emulsion.
将对比例1得到的偏氯乙烯乳液进行性能测试，结果如表1所示。The vinylidene chloride emulsion obtained in Comparative Example 1 was subjected to a performance test, and the results are shown in Table 1.
表1Table 1
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。对于本技术领域的普通技术人员来说，在不脱离本发明远离的前提下，还可以对本发明进行改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. For those skilled in the art, the present invention can also be improved and modified without departing from the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
对于所公开的实施例的说明，使本领域的技术人员可以实现或者使用本发明。对上述实施例的修改对于本领域的技术人员来讲是易于实施的，本文中所定义的原理可在不脱离本发明的范围的情况下，在其它实施例中实现。因此本发明将不受限于上述实施例，而是符合本文所公开的原理及特点一致的最宽的范围。The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Modifications to the above-described embodiments will be readily implemented by those skilled in the art, and the principles defined herein may be implemented in other embodiments without departing from the scope of the present invention. Therefore, the present invention is not limited to the above-mentioned embodiments, but conforms to the broadest scope consistent with the principles and features disclosed herein.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910857451.XA CN110511315A (en) | 2019-09-11 | 2019-09-11 | A kind of high-barrier vinylidene chloride-acrylate emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910857451.XA CN110511315A (en) | 2019-09-11 | 2019-09-11 | A kind of high-barrier vinylidene chloride-acrylate emulsion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110511315A true CN110511315A (en) | 2019-11-29 |
Family
ID=68630604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910857451.XA Pending CN110511315A (en) | 2019-09-11 | 2019-09-11 | A kind of high-barrier vinylidene chloride-acrylate emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110511315A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704689A (en) * | 2020-06-29 | 2020-09-25 | 天津城建大学 | High-adhesion aqueous vinylidene chloride copolymer emulsion for metal surface and preparation method thereof |
| CN113024743A (en) * | 2021-03-08 | 2021-06-25 | 青海洁神环境能源产业有限公司 | Two-component PVDC latex for biological rotating disc |
| CN116769362A (en) * | 2023-06-21 | 2023-09-19 | 浙江衢州巨塑化工有限公司 | Preparation method of PVDC emulsion for medicine packaging |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135450A (en) * | 2018-07-16 | 2019-01-04 | 天津市宝德包装有限公司 | A kind of food pack PVDC-MA high-barrier gluing and preparation method thereof |
| CN109438608A (en) * | 2018-11-07 | 2019-03-08 | 长春工业大学 | A kind of preparation method of degradable dinner set metachloroethylene copolymer water-based emulsion |
-
2019
- 2019-09-11 CN CN201910857451.XA patent/CN110511315A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135450A (en) * | 2018-07-16 | 2019-01-04 | 天津市宝德包装有限公司 | A kind of food pack PVDC-MA high-barrier gluing and preparation method thereof |
| CN109438608A (en) * | 2018-11-07 | 2019-03-08 | 长春工业大学 | A kind of preparation method of degradable dinner set metachloroethylene copolymer water-based emulsion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704689A (en) * | 2020-06-29 | 2020-09-25 | 天津城建大学 | High-adhesion aqueous vinylidene chloride copolymer emulsion for metal surface and preparation method thereof |
| CN111704689B (en) * | 2020-06-29 | 2022-04-26 | 天津城建大学 | High-adhesion aqueous vinylidene chloride copolymer emulsion for metal surface and preparation method thereof |
| CN113024743A (en) * | 2021-03-08 | 2021-06-25 | 青海洁神环境能源产业有限公司 | Two-component PVDC latex for biological rotating disc |
| CN116769362A (en) * | 2023-06-21 | 2023-09-19 | 浙江衢州巨塑化工有限公司 | Preparation method of PVDC emulsion for medicine packaging |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110511315A (en) | A kind of high-barrier vinylidene chloride-acrylate emulsion and preparation method thereof | |
| CN103214628B (en) | A kind of acrylic resin modified and preparation method thereof for weatherability coating | |
| CN103059192B (en) | Polyvinyl dichloride (PVDC) latex used for interior and exterior wall coating materials and preparation method thereof and application thereof | |
| CN103554334B (en) | The monomer modified acrylate of internal plasticization/inorganic nano combined emulsion and preparation method thereof | |
| CN102134292B (en) | A kind of preparation method of high melt fluidity polyvinylidene fluoride | |
| CN103059197B (en) | Aqueous antiseptic metal undercoat polyvinyl dichloride (PVDC) copolymer emulsion and preparation method thereof and application | |
| CN103524667A (en) | Water-based pressure-sensitive adhesive for polyethylene protection film and polyethylene protection film and preparation method thereof | |
| CN110818829B (en) | High-water-resistance waterproof emulsion and preparation method thereof | |
| TW201538589A (en) | Aqueous organic silicon fluoro-containing polymer dispersion and method for manufacturing the same | |
| CN105273121A (en) | Preparation method of fluorine-containing polyvinylidene chloride emulsion for coating | |
| CN102174139B (en) | Method for preparing polytetrafluoroethylene resin for coating | |
| CN102504089B (en) | Preparation method of water-resistant acrylic ester core-shell emulsion | |
| CN109021886A (en) | A kind of heat insulation broken bridge aluminum profile protective film water-borne pressure sensitive adhesive and preparation method thereof | |
| CN106749876A (en) | A kind of fluoroacrylic resin and preparation method thereof | |
| CN103059195B (en) | Polyvinyl dichloride (PVDC) latex special for kraft paper used for food packaging and preparation method thereof and application thereof | |
| CN103059193B (en) | Special PVDC latex coating of cigarette film and its preparation method and application | |
| CN116769362A (en) | Preparation method of PVDC emulsion for medicine packaging | |
| CN113402639B (en) | Chlorination modification method for resin with high vinyl acetate content | |
| US11472941B2 (en) | Functional monomer comprising rare earth/metal compound, preparation method thereof, and method of using the same | |
| CN106366223B (en) | The preparation method of CPVC impact modifier | |
| CN102268115B (en) | Heating-free technology for producing polymer emulsion | |
| CN112143148A (en) | Polyvinyl alcohol film and preparation method thereof | |
| CN105542046B (en) | The preparation method of daiflon | |
| CN111410612A (en) | Reducing agent monomer used for redox preparation of styrene-acrylic emulsion at normal temperature and synthesis method thereof | |
| CN105820285B (en) | A kind of metachloroethylene copolymer latex of salt fog resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191129 |
|
| WD01 | Invention patent application deemed withdrawn after publication |