WO2023184748A1 - 一种苯丙乳液，其原料组合物及其制备方法和应用 - Google Patents

一种苯丙乳液，其原料组合物及其制备方法和应用 Download PDF

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WO2023184748A1
WO2023184748A1 PCT/CN2022/101300 CN2022101300W WO2023184748A1 WO 2023184748 A1 WO2023184748 A1 WO 2023184748A1 CN 2022101300 W CN2022101300 W CN 2022101300W WO 2023184748 A1 WO2023184748 A1 WO 2023184748A1
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styrene
acrylate
acrylic emulsion
monomer
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PCT/CN2022/101300
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English (en)
French (fr)
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王瑞杰
房迎春
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上海保立佳化学技术有限公司
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18—Homopolymers or copolymers of nitriles
    • C09D133/20—Homopolymers or copolymers of acrylonitrile
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

Definitions

  • the invention belongs to the field of styrene-acrylic emulsion, and particularly relates to a styrene-acrylic emulsion, its raw material composition and its preparation method and application.
  • Wall wallpapering is a decorative technique that has emerged in the past decade. Wallpapers of various patterns and patterns are applied to the wall neatly and regularly by heating. After wallpapering, no other processing is needed. The wallpapered room gives people a comfortable, soft and solemn feeling. It is increasingly favored by consumers for its excellent performance and pleasing appearance.
  • a medium treatment is usually required between the wallpaper and the wall.
  • the purpose is to seal the surface of the cement-based wall to prevent water seepage, efflorescence and other phenomena, which will cause varying degrees of damage to the wallpaper and affect the aesthetic effect.
  • this field urgently needs to develop a wallpaper emulsion that has a good sealing effect on the wall, can ensure that the wallpaper is firmly adhered, is not easy to fall off and bloom, and is environmentally friendly; it can still maintain good performance when the wall is damp and water seepage. closed effect.
  • the technical problem to be solved by the present invention is to overcome the poor sealing effect of the existing wallpaper pasting medium on the wall to a certain extent.
  • the wall is damp and water seeps, it cannot achieve a good sealing effect, thus Defects such as damage, shedding, efflorescence, and blooming of wallpaper are caused, and a styrene-acrylic emulsion, its raw material composition, its preparation method and application are provided.
  • the styrene-acrylic emulsion prepared by the present invention which can be used to prepare wallpaper pasting media, is a product with certain flexibility, high solid content, and extremely fine particle size. It can be prepared into soft glue and hard glue according to actual needs, and has good effect on cement base materials.
  • the invention provides a raw material composition for styrene-acrylic emulsion, which includes the following components by weight: 30 to 50 parts of acrylic soft monomer, 40 to 60 parts of hard monomer, and 3 to 6 parts of cross-linking monomer. , 1.5 to 2 parts of emulsifier, 0.3 to 0.6 parts of initiator, 0.1 to 0.4 parts of pH buffer;
  • the hard monomers include acrylate hard monomers, styrene and functional hard monomers; the functional hard monomers include acrylic acid and acrylonitrile; where the cross-linking monomers include epoxy monomers and cross-linking monomer A, which is a monomer containing amino groups and/or hydroxyl groups.
  • the acrylate soft monomer may include ethyl acrylate, n-butyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate, isooctyl methacrylate, and 2-hydroxyethyl acrylate.
  • One or more of the esters are preferably n-butyl acrylate and/or isooctyl acrylate.
  • the acrylate hard monomer may include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Tert-butyl ester, hexyl methacrylate, isobornyl methacrylate, isobornyl acrylate, isobutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-methacrylate - One or more hydroxypropyl esters, preferably methyl methacrylate.
  • the functional hard monomer does not contain at least one of acrylic acid and acrylonitrile, the particle size will become coarser, the stability will be poor, and the blocking effect will be reduced.
  • the epoxy monomer may include glycidyl methacrylate.
  • the cross-linking monomer A may include one or more of aminobenzoic acid, aminohydroxybenzoic acid, aminocarboxyaniline and aliphatic chain dihydroxy acid.
  • aminobenzoic acid may include 3,5-diaminobenzoic acid.
  • aminohydroxybenzoic acid may include 3-amino-4-hydroxybenzoic acid.
  • the aliphatic chain dihydroxy acid may include 2,2-dihydroxymethylpropionic acid.
  • the emulsifier may include any one or more of fatty alcohol polyoxyethylene ethers, isomeric alcohol polyoxyethylene ethers, and fatty alcohol polyoxyethylene ether sulfates.
  • the fatty alcohol polyoxyethylene ether sulfate may include fatty alcohol polyoxyethylene ether sodium sulfate and/or fatty alcohol polyoxyethylene ether ammonium sulfate.
  • the emulsifier does not include alkylphenol ethoxylates.
  • the initiator may include persulfate and/or azo initiators.
  • the persulfate may include ammonium persulfate.
  • the pH buffer may include sodium bicarbonate and/or sodium carbonate.
  • the weight portion of the acrylate hard monomer may be 30 to 50 parts, preferably 40 to 45 parts.
  • the weight parts of styrene may be 5 to 15 parts, preferably 5 to 10 parts.
  • the weight portion of the functional hard monomer can be 5 to 12 parts, preferably 9 to 10 parts.
  • the weight ratio of the acrylic acid and the acrylonitrile may be 1: (1-2.5), preferably 1: (1.5-2.3).
  • the molar ratio of the epoxy monomer and the cross-linking agent A may be (1.5-3.5):1, preferably (2-2.7):1, such as 2.3:1.
  • the weight parts of the acrylate soft monomer are preferably 45 to 50 parts.
  • the weight portion of the cross-linking monomer is preferably 3 to 4.3 parts.
  • the weight part of the initiator is preferably 0.3 to 0.55 parts.
  • the weight part of the pH buffering agent is preferably 0.1 to 0.2 parts.
  • the raw material composition of the styrene-acrylic emulsion may further include a solvent.
  • the solvent can be a solvent commonly used in this field, preferably water, more preferably deionized water.
  • the weight parts of the solvent can be conventional in this field, preferably 50 to 100 parts, more preferably 70 to 90 parts.
  • the present invention also provides a method for preparing a styrene-acrylic emulsion, the raw materials of which include the raw material composition of the styrene-acrylic emulsion as described above, and the preparation method includes the following steps:
  • step (1) during the research and development process, it was found that the acrylate soft monomer, the hard monomer and the cross-linking monomer need to be added in order, otherwise the emulsification effect will be unsatisfactory and the system will easily stratify.
  • step (1) the preparation method of the mixture of the emulsifier, the pH buffer and the solvent can be conventional in the art. Generally, the emulsifier, the pH buffer and the solvent are mixed evenly. .
  • step (1) the mixing can be carried out under stirring conditions according to the routine in the art, and the stirring speed can be the routine in the art, preferably 200 to 300 rpm, more preferably 200 to 250 rpm.
  • the mixing time can be a conventional time for such operations in this field. Generally, it is enough to fully emulsify the system, preferably 20 to 30 minutes.
  • the mixing temperature can be a conventional temperature for this type of operation in the art, preferably 25 to 30°C.
  • step (2) some of the pre-emulsions may be mixed with a solvent before use.
  • the weight ratio of part of the pre-emulsion and the solvent may be 1:(2-4), preferably 1:(3-4).
  • the mixing can be carried out under stirring conditions according to common practice in this field, and the rotating speed of the stirring can be 100-150 rpm, preferably 100-120 rpm.
  • the mixing temperature may be a conventional temperature for such operations in this field, preferably 75-80°C, more preferably 78-80°C.
  • the mixing time may be a conventional time for such operations in this field, and generally it is enough to make the system evenly mixed.
  • the mixing reaction time can be a conventional time for such operations in this field. Generally, it is enough to fully emulsify the system, preferably 0.5 to 5 hours, more preferably 0.5 to 1 hour.
  • the temperature of the mixing reaction can be a conventional temperature for this type of operation in the art, preferably 75-80°C, and more preferably 78°C.
  • the mixing reaction time can be a conventional time for such operations in this field, preferably 0.5 to 3 hours, and more preferably 1 hour.
  • the temperature of the mixed reaction can be a conventional temperature for such operations in this field, preferably 85 to 88°C.
  • the operation of the mixing reaction may further include any one or more of cooling, adjusting the pH value of the system to 7.5-8, and filtration.
  • the conditions and methods for cooling can be conventional in the art, and generally can be cooling to 40-50°C.
  • the method of adjusting the pH value of the price system to 7.5-8 can be conventional in this field.
  • ammonia water can be used to adjust the pH value of the system to 7.5-8.
  • the weight parts ratio of part of the pre-emulsion in step (2) to the remaining part of the pre-emulsion in step (3) may be 1:(7-16), preferably 1:(9) ⁇ 14).
  • part of the initiator described in step (2) and/or the remaining part of the initiator described in step (3) can be added in the form of an initiator solution according to routine in the art.
  • the solvent in the initiator solvent may be a solvent commonly used in the art that can completely dissolve the initiator, preferably water, and more preferably deionized water.
  • the mass percentage of the initiator in the initiator solution can be 10% to 20%, preferably 15%.
  • the weight parts ratio of part of the initiator in step (2) to the remaining part of the initiator in step (3) can be 1: (2-3), preferably 1: (2) ⁇ 2.6).
  • the present invention also provides a styrene-acrylic emulsion, which is prepared by the above-mentioned preparation method of styrene-acrylic emulsion.
  • the present invention also provides the application of the above-mentioned styrene-acrylic emulsion as a raw material in preparing wallpaper pasting medium, interior wall paint and exterior wall paint.
  • the present invention also provides a wallpaper pasting medium, which includes the styrene-acrylic emulsion as mentioned above.
  • the wallpaper pasting medium may further include film-forming aids and/or thickeners.
  • the mass percentage of the film-forming assistant in the wallpaper pasting medium can be conventional in this field, preferably 3% to 8%.
  • the reagents and raw materials used in the present invention are all commercially available.
  • the positive and progressive effect of the present invention is that the styrene-acrylic emulsion prepared by the present invention, which can be used to prepare wallpaper pasting medium, is a product with certain flexibility, high solid content, and extremely fine particle size, and can be prepared into soft glue according to actual needs. and hard glue; at the same time, the styrene-acrylic emulsion prepared by the present invention still has good adhesion and sealing properties to the cement base material without using alkylphenol polyoxyethylene ether, and shows good water resistance and alkali resistance. , the water resistance is much higher than that of emulsion products on the market, and the release of VOCs including formaldehyde is low. It is a relatively environmentally friendly styrene-acrylic emulsion with extremely high industrial application prospects and promotion value.
  • This embodiment provides a styrene-acrylic emulsion with good water resistance and alkali resistance that can be used as a wallpaper pasting medium.
  • the types and weight parts of each component in the raw material are shown in Table 1:
  • the preparation method of styrene-acrylic emulsion includes the following steps:
  • step 2 Weigh 15 parts of the pre-emulsion obtained in step 1, add 30 parts of deionized water to the condensation stirring device, stir at 100 rpm and heat it up to 78°C, weigh one third of the initiator aqueous solution obtained in step 1 (where, (0.1 part of initiator), mix and react at 78°C for 0.5h to obtain a blue phase seed emulsion;
  • step 3 Within 2 hours, simultaneously add the remaining part of the pre-emulsion obtained in step 1 and the remaining part of the initiator aqueous solution obtained in step 1 (including 0.2 parts of initiator) to the blue phase seed emulsion obtained in step 2, and heat it to 85°C before reacting After 1 hour, cool down to 40°C and adjust the pH to 7.5 with ammonia water. After stirring evenly, filter and discharge the material to obtain the wallpaper pasting medium styrene acrylic emulsion.
  • This embodiment provides a styrene-acrylic emulsion with good water resistance and alkali resistance that can be used as a wallpaper pasting medium.
  • the types and weight parts of each component in the raw material are shown in Table 2:
  • the preparation method of styrene-acrylic emulsion includes the following steps:
  • step 2 Weigh 10 parts of the pre-emulsion obtained in step 1, add 40 parts of deionized water to the condensation stirring device, stir at 120 rpm and raise the temperature to 80°C, weigh part of the initiator aqueous solution obtained in step 1 (wherein, the initiator is 0.15 parts), mix and react at 80°C for 1 hour to obtain a blue phase seed emulsion;
  • step 3 (3) Within 3 hours, simultaneously add the remaining part of the pre-emulsion obtained in step 1 and the remaining part of the initiator aqueous solution obtained in step 1 (0.4 parts of the initiator) to the blue phase seed emulsion obtained in step 2, and heat it to 88°C before reacting After 1 hour, cool down to 50°C and adjust the pH to 8 with ammonia water. After stirring evenly, filter and discharge the material to obtain the wallpaper pasting medium styrene acrylic emulsion.
  • a styrene-acrylic emulsion including the following raw materials in parts by weight: 52 parts of acrylic soft monomer, 45 parts of acrylic hard monomer, 2.9 parts of cross-linking monomer, 1.5 parts of emulsifier, 0.3 parts of initiator, pH 0.1 part of buffer and 71.7 parts of water.
  • the acrylate soft monomer is a mixture of n-butyl acrylate and isooctyl acrylate.
  • the acrylate hard monomer is methyl methacrylate.
  • the cross-linking monomer is a mixture of diacetone acrylamide and diaminobenzoic acid, and the molar ratio of the two is 2:1.
  • the emulsifier is fatty alcohol polyoxyethylene ether ammonium sulfate, the initiator is ammonium persulfate, and the pH buffer is sodium bicarbonate.
  • the preparation method of styrene-acrylic emulsion includes the following steps:
  • Step 1 Dissolve the initiator in 1.7 parts by weight of deionized water to obtain an initiator aqueous solution; add 1.5 parts of fatty alcohol polyoxyethylene ether ammonium sulfate emulsifier and 0.1 part of sodium bicarbonate to 40 parts of deionized water, After mixing until completely dissolved, add 47 parts of n-butyl acrylate, 5 parts of isooctyl acrylate, 45 parts of methyl methacrylate, and 2.9 parts of cross-linking monomer, and stir for 30 minutes at 200 rpm to obtain a pre-emulsion;
  • Step 2 Weigh 17.6wt% of the pre-emulsion obtained in step 1, add 30 parts of deionized water to the condensation stirring device, stir at a rotating speed and raise the temperature to 78°C, weigh 0.1 part of the initiator aqueous solution obtained in step 1, and stir at 78°C React for 0.5h to obtain blue phase seed emulsion;
  • Step 3 Within 2 hours, simultaneously add the remaining pre-emulsion obtained in Step 1 and 0.2 part of the initiator aqueous solution to the blue-phase seed emulsion obtained in Step 2, raise the temperature to 85°C and react for 1 hour. After cooling to 40°C, adjust the pH with ammonia water to 7.5. After stirring evenly, filter and discharge the material to obtain pure acrylic emulsion for fabric foam coating.
  • This embodiment provides a styrene-acrylic emulsion with good water resistance and alkali resistance that can be used as a wallpaper pasting medium.
  • the types and weight parts of each component in the raw materials are shown in Table 3:
  • the preparation method of styrene-acrylic emulsion includes the following steps:
  • step 2 Weigh 13 parts of the pre-emulsion obtained in step 1, add 40 parts of deionized water to the condensation stirring device, stir at 150 rpm and heat it up to 80°C, weigh part of the initiator aqueous solution obtained in step 1 (wherein, the initiator is 0.2 parts), mix and react at 80°C for 1 hour to obtain a blue phase seed emulsion;
  • step 3 (3) Within 3 hours, simultaneously add the remaining part of the pre-emulsion obtained in step 1 and the remaining part of the initiator aqueous solution obtained in step 1 (0.3 parts of the initiator) to the blue phase seed emulsion obtained in step 2, and heat it to 88°C before reacting After 1 hour, cool down to 50°C and adjust the pH to 8 with ammonia water. After stirring evenly, filter and discharge the material to obtain the wallpaper pasting medium styrene acrylic emulsion.
  • Appearance color test The styrene-acrylic emulsion prepared in the above-mentioned Examples 1-2 and the commercially available styrene-acrylic emulsion in Comparative Example 1 were evaluated for appearance color. The results showed that the styrene-acrylic emulsion prepared in the above-mentioned Examples 1-2 was coated on All the products on the wall were milky white and slightly blue. The commercial product in Comparative Example 1 was milky white or milky blue after being applied on the wall.
  • Water resistance and alkali resistance test Apply the styrene acrylic emulsion prepared in the above Examples 1 to 3, the commercially available styrene acrylic emulsion in Comparative Example 1, and the products prepared in Comparative Example 2 and Comparative Example 3 on the same cement board. , the coating thickness is 0.2mm, and left at room temperature for 24 hours to form a paint film. Place the samples in tap water and 10% sodium hydroxide aqueous solution respectively, and observe the abnormality, flooding, and shedding time of the paint film. The test cycle is 48 hours. The results are shown in Table 4; wherein, each group in Example 1 and Example 2 is set up with 3 parallel experiments.
  • the wallpaper paste medium styrene acrylic emulsion prepared by the present invention has no abnormality in the coating after being immersed in water for 48 hours, and is only slightly bluish; in the alkali resistance test, there are no abnormalities for 7 days, and it is water and alkali resistant.
  • the performance is much higher than the styrene-acrylic emulsion products on the market and the products prepared in Comparative Examples 2 to 3.

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Abstract

本发明公开了一种苯丙乳液，其原料组合物及其制备方法和应用。苯丙乳液的原料组合物包括如下重量份数的各组分：30～50份丙烯酸酯软单体、40～60份硬单体、3～6份交联单体、1.5～2份乳化剂、0.3～0.6份引发剂、0.1～0.4份pH缓冲剂；硬单体包括丙烯酸酯硬单体、苯乙烯和功能性硬单体；功能性硬单体包括丙烯酸和丙烯腈；交联单体包括环氧基单体和交联单体A，交联单体A为含氨基和/或羟基的单体。本发明制得的苯丙乳液属于有一定柔韧度、固含量高、粒径极细的产品，对水泥基材具有良好的附着力及封闭性，表现出良好的耐水和耐碱性能，属于一种相对环保的苯丙乳液，具有极高的工业应用前景和推广价值。

Description

一种苯丙乳液，其原料组合物及其制备方法和应用
[根据细则26改正 11.07.2022]
本申请要求申请日为2022年03月29日的中国专利申请2022103200860的优先权。本申请引用上述中国专利申请的全文。
技术领域
[根据细则26改正 11.07.2022]
本发明属于苯丙乳液领域，特别涉及一种苯丙乳液，其原料组合物及其制备方法和应用。
背景技术
[根据细则26改正 11.07.2022]
墙壁贴壁纸是近十年出现的一种装饰工艺，是将各种花纹和图案的壁纸，采用加热的方式，整齐规则的贴附在墙面上。经过贴壁纸后，不需要再做其他的处理，贴过壁纸的房间给人舒适、柔和和庄重的感觉，以其优异的性能和令人赏心悦目的外观而越来越受到消费者的青睐。
[根据细则26改正 11.07.2022]
在壁纸与墙壁之间，通常需要进行一道介质处理，目的是对水泥基的墙体进行表面封闭，防止出现渗水，泛碱等现象，对壁纸造成不同程度的破坏,影响到美观的效果。目前市场上可作为粘贴介质的产品良莠不齐，部分有采用普通苯丙乳液作为壁纸粘贴介质，加入水进行刷涂，也有采用801胶水混搭乳液进行刷涂，这些产品在某种程度上对墙体的封闭效果不好，在墙体出现潮湿，渗水等情况时，不能很好地起到封闭效果，从而造成壁纸的破坏，例如，可能会导致壁纸出现脱落、泛碱和发花等问题。还有很多粘贴介质产品没有考虑到环保方面的问题，比如含有烷基酚聚氧乙烯醍类化合物(APEO)或含有过量的游离甲醛等，对环境和人都会造成不同程度的影响。
因此，本领域亟需研发一种对墙体封闭效果良好，可保证壁纸粘贴牢固，不易脱落、发花，且环保的壁纸用乳液；当墙体出现潮湿和渗水等现象时也依然能保持良好封闭效果。
发明内容
本发明要解决的技术问题是克服采用现有壁纸粘贴介质在某种程度上对墙体的封闭效果不好，在墙体出现潮湿和渗水等情况时，不能很好地起到封闭效果，从而造成壁纸出现破坏、脱落、泛碱和发花等缺陷，而提供一种苯丙乳液，其原料组合物及其制备方法和应用。本发明制得的可用于制备壁纸粘贴介质的苯丙乳液属于有一定柔韧度、固含量高、粒径极细的产品，可根据实际需求制备成软胶和硬胶，对水泥基材具有良好的附着力及封闭性，表现出良好的耐水和耐碱性能，耐水性能远高于市场在售乳液产品，并且VOC的释放量较低，属于一种相对环保的苯丙乳液，具有极高的工业应用前景和推广价值。
本发明采用以下技术方案解决上述技术问题：
本发明提供一种苯丙乳液的原料组合物，其包括如下重量份数的各组分：30～50份丙烯酸酯软单体、40～60份硬单体、3～6份交联单体、1.5～2份乳化剂、0.3～0.6份引发剂、0.1～0.4份pH缓冲剂；
其中，所述硬单体包括丙烯酸酯硬单体、苯乙烯和功能性硬单体；所述功能性硬单体包括丙烯酸和丙烯腈；其中，所述交联单体包括环氧基单体和交联单体A，所述交联单体A为含氨基和/或羟基的单体。
一些实施例中，所述丙烯酸酯软单体可包括丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正辛酯、丙烯酸异辛酯、丙烯酸月桂酯、甲基丙烯酸异辛酯、丙烯酸-2-羟乙酯中的一种或多种，较佳地为丙烯酸正丁酯和/或丙烯酸异辛酯。
一些实施例中，所述丙烯酸酯硬单体可包括甲基丙烯酸甲酯、甲基丙烯 酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸异冰片酯、丙烯酸异冰片酯、丙烯酸异丁酯、丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟乙酯和甲基丙烯酸-2-羟丙酯中的一种或多种，较佳地为甲基丙烯酸甲酯。
研发过程中发现，当所述功能性硬单体不含有丙烯酸和丙烯腈中至少一种时，会导致粒径变粗，稳定性差，封闭效果降低。
一些实施例中，所述环氧基单体可包括甲基丙烯酸环氧丙酯。
一些实施例中，所述交联单体A可包括氨基苯甲酸、氨基羟基苯甲酸、氨基羧基苯胺和脂肪链二羟基酸中的一种或多种。
其中，所述氨基苯甲酸可包括3，5-二氨基苯甲酸。
其中，所述氨基羟基苯甲酸可包括3-氨基-4-羟基苯甲酸。
其中，所述脂肪链二羟基酸可包括2，2-二羟甲基丙酸。
一些实施例中，所述乳化剂可包括脂肪醇聚氧乙烯醚、异构醇聚氧乙烯醚和脂肪醇聚氧乙烯醚硫酸盐中的任意一种或多种。
其中，所述脂肪醇聚氧乙烯醚硫酸盐可包括脂肪醇聚氧乙烯醚硫酸钠和/或脂肪醇聚氧乙烯醚硫酸铵。
一些实施例中，所述乳化剂不包括烷基酚聚氧乙烯醚。
一些实施例中，所述引发剂可包括过硫酸盐和/或偶氮类引发剂。
其中，所述过硫酸盐可包括过硫酸铵。
一些实施例中，所述pH缓冲剂可包括碳酸氢钠和/或碳酸钠。
一些实施例中，所述丙烯酸酯硬单体的重量份数可为30～50份，较佳地为40～45份。
一些实施例中，所述苯乙烯的重量份数可为5～15份，较佳地为5～10份。
一些实施例中，所述功能性硬单体的重量份数可为5～12份，较佳地为9～10份。
一些实施例中，所述丙烯酸和所述丙烯腈的重量份数比可为1：(1～2.5)，较佳地为1：(1.5～2.3)。
一些实施例中，所述环氧基单体和所述交联剂A的摩尔比可为(1.5～3.5)：1，较佳地为(2～2.7)：1，例如2.3：1。
一些实施例中，所述丙烯酸酯软单体的重量份数较佳地为45～50份。
一些实施例中，所述交联单体的重量份数较佳地为3～4.3份。
一些实施例中，所述引发剂的重量份数较佳地为0.3～0.55份。
一些实施例中，所述pH缓冲剂的重量份数较佳地为0.1～0.2份。
一些实施例中，所述苯丙乳液的原料组合物中还可进一步包括溶剂。
其中，所述溶剂可为本领域常规使用的溶剂，较佳地为水，更佳地为去离子水。
其中，所述溶剂的重量份数可为本领域常规，较佳地为50～100份，更佳地为70～90份。
本发明还提供一种苯丙乳液的制备方法，其原料包括如上所述的苯丙乳液的原料组合物，制备方法包括如下步骤：
(1)所述乳化剂、所述pH缓冲剂和溶剂的混合物中依次加入所述丙烯酸酯软单体、所述硬单体和所述交联单体，混合，得预乳液；
(2)部分所述预乳液与部分所述引发剂混合反应，制得种子乳液；
(3)所述种子乳液、剩余部分所述预乳液和剩余部分所述引发剂经混合反应，即可。
步骤(1)中，研发过程中发现所述丙烯酸酯软单体、所述硬单体和所述交联单体需按照顺序依次加入，否则会导致乳化效果不理想，容易导致体系分层。
步骤(1)中，所述乳化剂、所述pH缓冲剂和溶剂的混合物的制备方法可为本领域常规，一般将所述乳化剂、所述pH缓冲剂和所述溶剂混合均匀， 即可。
步骤(1)中，所述混合可按照本领域常规在搅拌的条件下进行，所述搅拌的转速可为本领域常规，较佳地为200～300rpm，更佳地为200～250rpm。
步骤(1)中，所述混合的时间可为本领域该类操作常规的时间，一般可使体系充分乳化即可，较佳地为20～30min。
步骤(1)中，所述混合的温度可为本领域该类操作常规的温度，较佳地为25～30℃。
步骤(2)中，部分所述预乳液在使用前还可先与溶剂混合。
其中，部分所述预乳液和所述溶剂的重量份数比可为1：(2～4)，较佳地为1:(3～4)。
其中，所述混合可按照本领域常规在搅拌的条件下进行，所述搅拌的转速可为100～150rpm，较佳地为100～120rpm。
其中，所述混合的温度可为本领域该类操作常规的温度，较佳地为75～80℃，更佳地为78～80℃。
其中，所述混合是时间可为本领域该类操作常规的时间，一般使体系混合均匀即可。
步骤(2)中，所述混合反应的时间可为本领域该类操作常规的时间，一般可使体系充分乳化即可，较佳地为0.5～5h，更佳地为0.5～1h。
步骤(2)中，所述混合反应的温度可为本领域该类操作常规的温度，较佳地为75～80℃，更佳地为78℃。
步骤(3)中，所述混合反应的时间可为本领域该类操作常规的时间，较佳地为0.5～3h，更佳地为1h。
步骤(3)中，所述混合反应的温度可为本领域该类操作常规的温度，较佳地为85～88℃。
步骤(3)中，所述混合反应的操作后还可进一步包括降温、调节体系 的pH值至7.5～8和过滤中任意一种或多种的操作。
其中，所述降温的条件和方法可为本领域常规，一般可为降温至40～50℃。
其中，调价体系的pH值至7.5～8的方法可为本领域常规，一般可采用氨水调节体系的pH值至7.5～8。
一些实施例中，步骤(2)中部分所述预乳液与步骤(3)中剩余部分所述预乳液的重量份数比可为1：(7～16)，较佳地为1:(9～14)。
一些实施例中，步骤(2)中部分所述引发剂和/或步骤(3)中剩余部分所述引发剂可按照本领域常规以引发剂溶液的方式添加。
其中，所述引发剂溶剂中的溶剂可为本领域常规使用的可将所述引发剂完全溶解的溶剂，较佳地为水，更佳地为去离子水。
其中，所述引发剂溶液中，所述引发剂占所述引发剂溶液的质量百分比可为10％～20％，较佳地为15％。
一些实施例中，步骤(2)中部分所述引发剂与步骤(3)中剩余部分所述引发剂的重量份数比可为1：(2～3)，较佳地为1：(2～2.6)。
本发明还提供一种苯丙乳液，其由如上所述的苯丙乳液的制备方法制得。
本发明还提供一种如上所述的苯丙乳液作为原料在制备壁纸粘贴介质、内墙涂料和外墙涂料中的应用。
本发明还提供一种壁纸粘贴介质，其包括如上所述的苯丙乳液。
一些实施例中，所述壁纸粘贴介质中还可进一步包括成膜助剂和/或增稠剂。
其中，所述成膜助剂占所述壁纸粘贴介质的质量百分比可为本领域常规，较佳地为3％～8％。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：本发明制得的可用于制备壁纸粘贴介质的苯丙乳液属于一种有一定柔韧度、固含量高、粒径极细的产品，可根据实际需求制备成软胶和硬胶；同时本发明制得的苯丙乳液在不使用烷基酚聚氧乙烯醚的条件下，对水泥基材依然具有良好的附着力及封闭性，表现出良好的耐水和耐碱性能，耐水性能远高于市场在售乳液产品，并且包括甲醛在内的VOC的释放量较低，属于一种相对环保的苯丙乳液，具有极高的工业应用前景和推广价值。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
实施例1
本实施例提供一种耐水、耐碱性能良好的可作为壁纸粘贴介质的苯丙乳液，原料中各组分种类和重量份数见表1：
表1
Figure PCTCN2022101300-appb-000001
Figure PCTCN2022101300-appb-000002
苯丙乳液的制备方法包括以下步骤：
(1)按重量份，将0.3份引发剂溶解于1.7份的去离子水中，得到引发剂水溶液；将1.5份脂肪醇聚氧乙烯醚硫酸铵乳化剂和0.1份碳酸氢钠加入40份去离子水中，混合至完全溶解后，加入30份丙烯酸正丁酯和15份丙烯酸异辛酯，再加入40份甲基丙烯酸甲酯、10份苯乙烯、4份丙烯酸和6份丙烯腈，最后加入2份甲基丙烯酸环氧丙酯和0.9份的3，5-二氨基苯甲酸，在200rpm转速下搅拌30min后，得到预乳液；
(2)称取15份步骤1所得预乳液，30份去离子水加入冷凝搅拌装置中，在100rpm转速下搅拌升温至78℃后，称取三分之一步骤1所得引发剂水溶液(其中，引发剂为0.1份)，在78℃下混合反应0.5h，得到蓝相种子乳液；
(3)在2h内，向步骤2所得蓝相种子乳液中同时加入剩余部分步骤1所得预乳液和剩余部分步骤1所得引发剂水溶液(其中，引发剂为0.2份)，升温至85℃后反应1h，降温至40℃后用氨水调节pH至7.5，搅拌均匀后，过滤、出料，即得壁纸粘贴介质苯丙乳液。
实施例2
本实施例提供一种耐水、耐碱性能良好的可作为壁纸粘贴介质的苯丙乳液，原料中各组分种类和重量份数见表2：
表2
Figure PCTCN2022101300-appb-000003
Figure PCTCN2022101300-appb-000004
苯丙乳液的制备方法包括以下步骤：
(1)按重量份，将0.55份引发剂溶解于3.1份的去离子水中，得到引发剂水溶液；将2份脂肪醇聚氧乙烯醚硫酸钠乳化剂和0.2份碳酸氢钠加入45份去离子水中混合至完全溶解后，加入40份丙烯酸正丁酯和5份丙烯酸异辛酯，再加入45份甲基丙烯酸甲酯、5份苯乙烯、3份丙烯酸和7份丙烯腈，最后加入3份甲基丙烯酸环氧丙酯和1.3份的3-氨基-4-羟基苯甲酸，在250rpm转速下搅拌30min后，得到预乳液；
(2)称取10份步骤1所得预乳液，40份去离子水加入冷凝搅拌装置中，在120rpm转速下搅拌升温至80℃后，称取部分步骤1所得引发剂水溶液(其中，引发剂为0.15份)，在80℃下混合反应1h，得到蓝相种子乳液；
(3)在3h内，向步骤2所得蓝相种子乳液中同时加入剩余部分步骤1所得预乳液和剩余部分步骤1所得引发剂水溶液(其中，引发剂为0.4份)，升温至88℃后反应1h，降温至50℃后用氨水调节pH至8，搅拌均匀后，过滤、出料，即得壁纸粘贴介质苯丙乳液。
对比例1
浙江新力化工有限公司生产的产品编号为XL200的苯丙乳液。
对比例2
提供一种苯丙乳液，按重量份计，包括如下原料：丙烯酸酯软单体52份、丙烯酸酯硬单体45份、交联单体2.9份、乳化剂1.5份、引发剂0.3份、pH缓冲剂0.1份、水71.7份。
所述丙烯酸酯软单体为丙烯酸正丁酯、丙烯酸异辛酯的混合物。所述丙烯酸酯硬单体为甲基丙烯酸甲酯。所述交联单体为双丙酮丙烯酰胺和二氨基苯甲酸的混合物，二者摩尔比为2：1。所述乳化剂为脂肪醇聚氧乙烯醚硫酸铵，所述引发剂为过硫酸铵，所述pH缓冲剂为碳酸氢钠。
苯丙乳液制备方法，包括以下步骤：
步骤一：按重量份，将引发剂溶解于1.7份的去离子水中，得到引发剂水溶液；将1.5份脂肪醇聚氧乙烯醚硫酸铵乳化剂和0.1份碳酸氢钠加入40份去离子水中，混合至完全溶解后，依次加入47份丙烯酸正丁酯、5份丙烯酸异辛酯、45份甲基丙烯酸甲酯、2.9份交联单体，在200rpm转速下搅拌30min后，得到预乳液；
步骤二：称取17.6wt％步骤一所得预乳液，30份去离子水加入冷凝搅拌装置中，在转速下搅拌升温至78℃后，称取0.1份步骤一所得引发剂水溶液，在78℃下反应0.5h，得到蓝相种子乳液；
步骤三：在2h内，向步骤二所得蓝相种子乳液中同时加入剩余的步骤一所得预乳液和0.2份引发剂水溶液，升温至85℃后反应1h，降温至40℃后用氨水调节pH至7.5，搅拌均匀后，过滤、出料，即得织物发泡涂层用纯丙乳液。
对比例3
本实施例提供一种耐水、耐碱性能良好的可作为壁纸粘贴介质的苯丙乳 液，原料中各组分种类和重量份数见表3：
表3
Figure PCTCN2022101300-appb-000005
苯丙乳液的制备方法包括以下步骤：
(1)按重量份，将0.5引发剂溶解于2.8份的去离子水中，得到引发剂水溶液；将2份脂肪醇聚氧乙烯醚硫酸钠乳化剂和0.2份碳酸氢钠加入50份去离子水中混合至完全溶解后，加入13份丙烯酸正丁酯和24份丙烯酸异辛酯，再加入45份甲基丙烯酸甲酯、10份苯乙烯、2份丙烯酸和8份丙烯腈，最后加入4份甲基丙烯酸环氧丙酯和1.5份的2，2-二羟甲基丙酸，在300rpm转速下搅拌20min后，得到预乳液；
(2)称取13份步骤1所得预乳液，40份去离子水加入冷凝搅拌装置中，在150rpm转速下搅拌升温至80℃后，称取部分步骤1所得引发剂水溶液(其中，引发剂为0.2份)，在80℃下混合反应1h，得到蓝相种子乳液；
(3)在3h内，向步骤2所得蓝相种子乳液中同时加入剩余部分步骤1所得预乳液和剩余部分步骤1所得引发剂水溶液(其中，引发剂为0.3份)，升温至88℃后反应1h，降温至50℃后用氨水调节pH至8，搅拌均匀后，过滤、出料，即得壁纸粘贴介质苯丙乳液。
效果实施例1
外观颜色测试：将上述实施例1～2制得的苯丙乳液和对比例1中市售苯丙乳液进行外观颜色评价，结果表明，上述实施例1～2制得的苯丙乳液涂敷在墙上后均为乳白微蓝色，对比例1中市售产品涂敷在墙上后为乳白色或乳白色蓝相。
耐水和耐碱性测试：将上述实施例1～3制得的苯丙乳液、对比例1中市售苯丙乳液、对比例2和对比例3中制得的产品涂抹在相同的水泥板上，涂抹厚度为0.2mm，常温放置24h，形成漆膜，将样品分别放于自来水和10％的氢氧化钠水溶液中，观察漆膜出现异常、泛滥和脱落时间，以48h为测试周期，结果见表4；其中，实施例1和实施例2中每组设置3个平行实验。
表4
Figure PCTCN2022101300-appb-000006
Figure PCTCN2022101300-appb-000007
综合上述实验结果可见：本发明制备得到的壁纸粘贴介质苯丙乳液，浸置水中48h涂膜无异常，仅轻微泛蓝；耐碱性实验中，7天也无异常，且其耐水和耐碱性能远高于市场在售苯丙乳液产品和对比例2～3制得的产品。
最后，还需要说明的是，在本发明中术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管上面已经通过本公开的具体实施例的描述对本公开进行了披露，但是，应该理解，本领域技术人员可在所附方案的精神和范围内设计对本公开的各种修改、改进或者等同物。这些修改、改进或者等同物也应当被认为包括在本公开所要求保护的范围内。

Claims (10)

  1. 一种苯丙乳液的原料组合物，其特征在于，其包括如下重量份数的各组分：30～50份丙烯酸酯软单体、40～60份硬单体、3～6份交联单体、1.5～2份乳化剂、0.3～0.6份引发剂、0.1～0.4份pH缓冲剂；
    其中，所述硬单体包括丙烯酸酯硬单体、苯乙烯和功能性硬单体；所述功能性硬单体包括丙烯酸和丙烯腈；其中，所述交联单体包括环氧基单体和交联单体A，所述交联单体A为含氨基和/或羟基的单体。
  2. 如权利要求1所述的苯丙乳液的原料组合物，其特征在于，所述苯丙乳液的原料组合物满足下述条件中至少一种：
    所述丙烯酸酯软单体包括丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正辛酯、丙烯酸异辛酯、丙烯酸月桂酯、甲基丙烯酸异辛酯、丙烯酸-2-羟乙酯中的一种或多种，较佳地为丙烯酸正丁酯和/或丙烯酸异辛酯；
    所述丙烯酸酯硬单体包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸异冰片酯、丙烯酸异冰片酯、丙烯酸异丁酯、丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟乙酯和甲基丙烯酸-2-羟丙酯中的一种或多种，较佳地为甲基丙烯酸甲酯；
    所述环氧基单体包括甲基丙烯酸环氧丙酯；
    所述交联单体A包括氨基苯甲酸、氨基羟基苯甲酸、氨基羧基苯胺和脂肪链二羟基酸中的一种或多种；较佳地，所述氨基苯甲酸包括3，5-二氨基苯甲酸；较佳地，所述氨基羟基苯甲酸包括3-氨基-4-羟基苯甲酸；较佳地，所述脂肪链二羟基酸包括2，2-二羟甲基丙酸；
    所述乳化剂包括脂肪醇聚氧乙烯醚、异构醇聚氧乙烯醚和脂肪醇聚氧乙烯醚硫酸盐中的任意一种或多种；较佳地，所述脂肪醇聚氧乙烯醚硫酸盐包 括脂肪醇聚氧乙烯醚硫酸钠和/或脂肪醇聚氧乙烯醚硫酸铵；
    所述乳化剂不包括烷基酚聚氧乙烯醚；
    所述引发剂包括过硫酸盐和/或偶氮类引发剂；较佳地，所述过硫酸盐包括过硫酸铵；所述pH缓冲剂包括碳酸氢钠和/或碳酸钠。
  3. 如权利要求1所述的苯丙乳液的原料组合物，其特征在于，所述苯丙乳液的原料组合物满足下述条件中至少一种：
    所述丙烯酸酯硬单体的重量份数为30～50份，较佳地为40～45份；
    所述苯乙烯的重量份数为5～15份，较佳地为5～10份；
    所述功能性硬单体的重量份数为5～12份，较佳地为9～10份；
    所述丙烯酸和所述丙烯腈的重量份数比为1：(1～2.5)，较佳地为1：(1.5～2.3)；
    所述环氧基单体和所述交联剂A的摩尔比为(1.5～3.5)：1，较佳地为(2～2.7)：1；
    所述丙烯酸酯软单体的重量份数为45～50份；
    所述交联单体的重量份数为3～4.3份；
    所述引发剂的重量份数为0.3～0.55份；
    所述pH缓冲剂的重量份数为0.1～0.2份。
  4. 如权利要求1～3中任意一项所述的苯丙乳液的原料组合物，其特征在于，所述苯丙乳液的原料组合物中还进一步包括溶剂；
    较佳地，所述溶剂为水，更佳地为去离子水；
    较佳地，所述溶剂的重量份数为50～100份，更佳地为70～90份。
  5. 一种苯丙乳液的制备方法，其特征在于，其原料包括如权利要求1～4中任意一项所述的苯丙乳液的原料组合物，制备方法包括如下步骤：
    (1)所述乳化剂、所述pH缓冲剂和溶剂的混合物中依次加入所述丙烯酸酯软单体、所述硬单体和所述交联单体，混合，得预乳液；
    (2)部分所述预乳液与部分所述引发剂混合反应，制得种子乳液；
    (3)所述种子乳液、剩余部分所述预乳液和剩余部分所述引发剂经混合反应，即可。
  6. 如权利要求5所述的苯丙乳液的制备方法，其特征在于，所述制备方法满足下述条件中至少一种：
    步骤(1)中，所述混合在搅拌的条件下进行，所述搅拌的转速为200～300rpm，较佳地为200～250rpm；
    步骤(1)中，所述混合的时间为20～30min；
    步骤(1)中，所述混合的温度为25～30℃；
    步骤(2)中，部分所述预乳液在使用前先与溶剂混合；较佳地，部分所述预乳液和所述溶剂的重量份数比为1：(2～4)，更佳地为1：(3～4)；较佳地，所述混合在搅拌的条件下进行，所述搅拌的转速为100～150rpm，更佳地为100～120rpm；较佳地，所述混合的温度为75～80℃，更佳地为78～80℃；
    步骤(2)中，所述混合反应的时间为0.5～5h，较佳地为0.5～1h；
    步骤(2)中，所述混合反应的温度为75～80℃，较佳地为78℃；
    步骤(3)中，所述混合反应的时间为0.5～3h，较佳地为1h；
    步骤(3)中，所述混合反应的温度为85～88℃；
    步骤(3)中，所述混合反应的操作后还进一步包括降温、调节体系的pH值至7.5～8和过滤中任意一种或多种的操作；较佳地，所述降温为降温至40～50℃；较佳地，采用氨水调节体系的pH值至7.5～8。
  7. 如权利要求5或6所述的苯丙乳液的制备方法，其特征在于，所述制备方法满足下述条件中至少一种：
    步骤(2)中部分所述预乳液与步骤(3)中剩余部分所述预乳液的重量份数比为1：(7～16)，较佳地为1：(9～14)；
    步骤(2)中部分所述引发剂和/或步骤(3)中剩余部分所述引发剂以引 发剂溶液的方式添加；较佳地，所述引发剂溶剂中的溶剂为水，更佳地为去离子水；较佳地，所述引发剂溶液中，所述引发剂占所述引发剂溶液的质量百分比为10％～20％，更佳地为15％；
    步骤(2)中部分所述引发剂与步骤(3)中剩余部分所述引发剂的重量份数比为1：(2～3)，较佳地为1：(2～2.6)。
  8. 一种苯丙乳液，其特征在于，其由如权利要求5～7中任意一项所述的苯丙乳液的制备方法制得。
  9. 一种如权利要求8所述的苯丙乳液作为原料在制备壁纸粘贴介质、内墙涂料和外墙涂料中的应用。
  10. 一种壁纸粘贴介质，其特征在于，其包括如权利要求8所述的苯丙乳液；
    较佳地，所述壁纸粘贴介质中还进一步包括成膜助剂和/或增稠剂；
    更佳地，所述成膜助剂占所述壁纸粘贴介质的质量百分比为3％～8％。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011012216A (ja) * 2009-07-03 2011-01-20 Toagosei Co Ltd エマルション組成物
CN110776591A (zh) * 2019-10-29 2020-02-11 上海保立佳新材料有限公司 用于织物复合的苯丙乳液胶黏剂及其制备方法
CN110983794A (zh) * 2019-12-02 2020-04-10 上海保立佳新材料有限公司 一种耐水性好的织物发泡涂层用纯丙乳液及其制备方法

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CN106478864B (zh) * 2016-11-24 2018-08-24 北京宝辰联合科技股份有限公司 一种低凝聚物防水乳液及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011012216A (ja) * 2009-07-03 2011-01-20 Toagosei Co Ltd エマルション組成物
CN110776591A (zh) * 2019-10-29 2020-02-11 上海保立佳新材料有限公司 用于织物复合的苯丙乳液胶黏剂及其制备方法
CN110983794A (zh) * 2019-12-02 2020-04-10 上海保立佳新材料有限公司 一种耐水性好的织物发泡涂层用纯丙乳液及其制备方法

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