CN101870757A - Reactive emulsifier soap-free styrene surface sizing agent and preparation method thereof - Google Patents

Reactive emulsifier soap-free styrene surface sizing agent and preparation method thereof Download PDF

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CN101870757A
CN101870757A CN 201010168868 CN201010168868A CN101870757A CN 101870757 A CN101870757 A CN 101870757A CN 201010168868 CN201010168868 CN 201010168868 CN 201010168868 A CN201010168868 A CN 201010168868A CN 101870757 A CN101870757 A CN 101870757A
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mass ratio
ammonium persulfate
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monomer mixture
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CN101870757B (en )
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付旭东
张国运
彭莉
徐永建
杨军胜
杨秀芳
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陕西科技大学
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Abstract

The invention discloses a reactive emulsifier soap-free styrene surface sizing agent and a preparation method thereof; the molecular structure of the reactive emulsifier soap-free styrene surface sizing agent is shown as the accompanying drawing. The preparation method of the reactive emulsifier soap-free styrene surface sizing agent comprises the following steps that: first, polyethylene glycol, stearic acid and maleic anhydride react to obtain maleic acid polyethylene glycol single-stearic acid ester; then ammonium persulfate serves as an initiator, and the maleic acid polyethylene glycol single-stearic acid ester, styrene, acrylamide, acrylic acid and acrylonitrile are prepared into the reactive emulsifier soap-free styrene surface sizing agent through copolymerization reaction; and the obtained reactive emulsifier soap-free styrene surface sizing agent eliminates the disadvantages and the pollution of small molecule emulsifier, and is characterized by excellent integration with fibers, reduced hair and powder drop, higher seizing degree, high surface strength, capability of adapting to high-speed printing and the like.

Description

一种反应型乳化剂无皂苯丙表面施胶剂及其制备方法 Emulsifier free styrene - acrylate surface sizing agent and method for preparing reactive

技术领域 FIELD

[0001] 本发明涉及轻型纸表面施胶剂的制备领域,特别涉及一种反应型乳化剂无皂苯丙表面施胶剂及其制备方法。 [0001] The present invention relates to the field of preparation of light paper surface sizing agent, particularly to a soap-free emulsifying reactive sizing agent and a preparation method benzenepropanoic surface.

背景技术 Background technique

[0002] 轻型纸是一种轻型胶版纸,它有着独特的生产加工工艺,不含荧光增白剂,纸张纤维比重轻、质地松厚、表面光滑、色泽柔和较适合于彩色书刊产品的印刷备受人们的青睐。 [0002] Light-paper is a lightweight offset paper, which has a unique production process, contain fluorescent brighteners, light paper fiber specific gravity, bulky texture, smooth surface, more suitable for printing color and soft color books product prepared by people of all ages. 由于轻型纸质地较轻,用它印刷的书刊比用普通纸印刷的书刊重量大约可以减轻20%-30%,既方便了读者的阅读,也较好地起到了降低物流成本的作用。 Since the paper to light the lighter, with its printing books and books with the weight ratio of plain paper printing can be reduced from about 20% -30%, both for the convenience of the reader to read, but also preferably reduced logistics costs play a role. 所以,轻型纸在印刷书刊、杂志方面取代了部分胶版纸、铜版纸的应用市场使生产成本也得到了一定程度的降低,深受市场的欢迎。 Therefore, light paper replaced in part offset paper printing books, magazines aspects, the application of coated paper market production costs have also been reduced to some extent, welcomed by the market. 轻型纸生产采用的浆料配比以化学机械浆为主,这些浆料中含有大量的木素,纤维比较挺硬、纤维间结合力较差,由于轻型纸的纤维组织较松弛,厚度相对较大,但是,它的抗张性能相对也较差一点,且极易受潮而产生变形情况。 Light paper pulp produced using the ratio of the main chemical mechanical pulp, which contains large amounts of slurry lignin, fibers are more stiff, the binding force between fibers is poor, because of the relatively light paper fibrous tissue relaxation, the thickness of the relatively large, however, it is also relatively poor tensile properties that moisture and easily deformed situation. 这些因素造成了纸页表面强度和平滑度下降,以致印刷过程中出现掉粉掉毛现象。 These factors contribute to the sheet surface smoothness and strength decrease, so that the powder out linting during printing occurs. 另一方面随着大量进口印刷机械的不断引进投产,纸品印刷过程中对纸张表面性能及吸墨性能提出了更高的要求, 对纸张的表面强度也提出更高的要求。 With the other hand the introduction of a large number of inlet production printing machine, the printing paper during the paper surface properties and a higher ink absorption performance requirements, the surface strength of the paper is also higher demands. 轻型纸传统的表面施胶剂有淀粉、氧化淀粉、磷酸酯淀粉、聚丙烯酰胺改性淀粉和聚乙烯醇等,它们在使用过程中存在着和纤维的亲和力较差、 成膜易断裂容易出现印刷过程中的掉毛、掉粉现象、抗水性较差、表面强度不够等缺点,使其适用的范围受到了限制。 Light paper with a conventional surface sizing starch, oxidized starch, phosphate starch, modified starch, polyacrylamide or polyvinyl alcohol, and they are a poor affinity for the fibers during use, prone to forming the scissile printing process lint, powder out phenomenon, poor water resistance, surface strength enough disadvantages, so the scope of application is limited. 目前开始使用苯丙乳液是由苯乙烯与丙烯酸酯单体通过乳液聚合制备的共聚物,其制备过程多使用小分子乳化剂,既影响轻型纸的耐水性能和成膜性能又存在环境污染。 Currently started with acrylic emulsion is a styrene acrylate monomer copolymer prepared by emulsion polymerization, the preparation process multiple small molecule emulsifiers, affect both the water resistance and film-forming properties of light paper and the presence of environmental pollution.

发明内容 SUMMARY

[0003] 为了克服上述现有技术的缺点,本发明的目的在于提供一种反应型乳化剂无皂苯丙表面施胶剂及其制备方法,所得的反应型乳化剂无皂苯丙表面施胶剂具有和纤维结合优良,减轻掉毛掉粉,改善施胶度,表面强度高和能适应高速印刷等特点。 [0003] In order to overcome the above disadvantages of the prior art, an object of the present invention is to provide a reactive emulsifier free styrene - acrylate surface sizing agent and method of preparation, the resulting reaction emulsifier free styrene - acrylate surface sizing and fibers having excellent binding agent, reduce linting, improve the degree of sizing, strength and high surface energy characteristics suitable for high speed printing and the like.

[0004] 为达到上述目的,本发明采用的技术方案为: [0004] To achieve the above object, the technical solution adopted by the invention is:

[0005] 一种反应型乳化剂无皂苯丙表面施胶剂的分子结构为: [0005] A molecular structure of the reactive emulsifier free styrene - acrylate surface sizing agent is:

[0006] [0006]

[0007] 反应型乳化剂无皂苯丙表面施胶剂 [0007] benzenepropanoic soap-free emulsifying agent reactive surface sizing agent

[0008] 其中x、y、z、m、n均为大于零的整数。 [0008] where x, y, z, m, n are integers greater than zero.

[0009] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法为:先由聚乙二醇、硬脂酸和顺丁烯二酸酐反应得到顺丁烯二酸聚乙二醇单硬酯酸酯,再以过硫酸铵为引发剂,由顺丁烯二酸聚乙二醇单硬脂酸酯与苯乙烯、丙烯酰胺、丙烯酸和丙烯腈通过共聚反应制备反应型乳化剂无皂苯丙表面施胶剂。 [0009] The method of preparing a soap-free emulsifying benzenepropanoic a reactive surface sizing agent is: first polyethylene glycol, stearic acid and maleic anhydride obtained by reacting maleic acid polyethylene glycol monostearate acrylate ester, and then ammonium persulfate as the initiator, a maleic acid polyethylene glycol monostearate and styrene, acrylamide, acrylic acid and acrylonitrile prepared by the copolymerization reaction of benzene soap-emulsifier propan surface sizing agent. 其反应过程如下: [0010] Reaction process is as follows: [0010]

[0019] 反应型乳化剂无皂苯丙表面施胶剂 [0019] benzenepropanoic soap-free emulsifying agent reactive surface sizing agent

[0020] 其中x、y、Z、m、n均为大于零的整数。 [0020] where x, y, Z, m, n are integers greater than zero.

[0021] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,具体包括以下步骤: [0021] A method for preparing reactive surface sizing agent benzenepropanoic soap emulsifier-free, includes the following steps:

[0022] 第一步,将聚乙二醇-400和硬脂酸加入第一反应器中在80_85°C时反应1. 5-2. O 小时,再加入顺丁烯二酸酐继续保温反应1. 0-1. 5小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5, [0022] The first step, the polyethylene glycol-400 stearate, and added to the first reactor 1. The reaction at 5-2 80_85 ° C. O h, then maleic anhydride was added the reaction was further incubated 1 . 0-15 hours to obtain a maleic acid polyethylene glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5

[0023] 第二步,将顺丁烯二酸聚乙二醇单硬脂酸酯、苯乙烯、丙烯酰胺、丙烯酸和丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体, [0023] The second step, maleic acid, polyethylene glycol monostearate, styrene, acrylamide, acrylic acid and acrylonitrile by 25: 5: 6: 3: 1 mass mixture ratio of blend monomer,

[0024] 第三步,将过硫酸铵和去离子水以质量比1 : 20制成过硫酸铵水溶液, [0024] The third step, ammonium persulfate and deionized water in a mass ratio of 1: 20 ammonium persulfate aqueous solution prepared,

[0025] 第四步,在第二反应器中加入去离子水,升温至60-70°C,去离子水和混合单体的质量比为124 : 40,再加入过硫酸铵水溶液和混合单体,过硫酸铵水溶液与混合单体的质量比为21 : 40,整个加料时间为1-2小时, [0025] The fourth step is added in the second reactor of deionized water, warmed to 60-70 ° C, mass of deionized water and the mixing ratio of the monomers is 124: 40, was added and mixing an aqueous solution of ammonium persulfate single body mass aqueous solution of ammonium persulfate and monomer mixture ratio of 21: 40, the entire addition time was 1-2 hours.

[0026] 第五步,加料完毕后于80_90°C保温反应2. 0-3. O小时, [0026] The fifth step, after the addition was complete the reaction was kept 80_90 ° C 2. 0-3. O h,

[0027] 第六步,降温到20-30°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 0-7. 0,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 [0027] The sixth step, cooled to 20-30 ° C, 30% sodium hydroxide solution adjusted to pH 5. 0-7. 0, the mass fraction of the material, to obtain a reaction-free soap emulsifier benzenepropanoic surface sizing agent.

[0028] 由于一种反应型乳化剂无皂苯丙表面施胶剂中不残留小分子乳化剂,具有和纤维结合优良,减轻掉毛掉粉,改善施胶度,表面强度高和能适应高速印刷等特点。 [0028] Since one reactive emulsifier free styrene - acrylate surface sizing agent does not remain small molecule emulsifier, and fibers having excellent binding, reduce linting, improve the degree of sizing, strength, and can adapt to high-speed surface printing and other features. 具体实施方式 detailed description

[0029] 下面将以具体实施例对本发明的方法作进一步详细的描述。 [0029] The following will the specific embodiments of the method of the present invention will be described in further detail.

[0030] 实施例一 [0030] Example a

[0031] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,具体包括以下步骤: [0031] A method for preparing reactive surface sizing agent benzenepropanoic soap emulsifier-free, includes the following steps:

[0032] 第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在80°C时反应1. 5 小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 0小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5, [0032] The first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor in the reactor at 80 ° C 1. 5 hours together with 2.5 g of maleic anhydride the reaction incubation was continued for 1.0 hours, to give maleic acid, polyethylene glycol monostearate, polyethylene glycol-400 of said mass stearic acid and maleic anhydride in the ratio of 10: 7: 2.5

[0033] 第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体, [0033] The second step, 25 g of maleic acid and polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing,

[0034] 第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, [0034] The third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared,

[0035] 第四步,在第二反应器中加入124克去离子水,升温至60°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : 40,整个加料时间为1小时, [0035] The fourth step, in the second reactor was added 124 grams of deionized water, warmed to 60 ° C, deionized water and the mass ratio of the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution 40 g monomer mixture, an aqueous solution of ammonium persulfate and monomer mixture mass ratio of 21: 40, the entire addition time was 1 hour,

[0036] 第五步,加料完毕后于80°C保温反应2. 0小时, [0036] The fifth step, after the addition was complete the reaction was kept 80 ° C 2.0 hours,

[0037] 第六步,降温到20°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 0,出料, 得到反应型乳化剂无皂苯丙表面施胶剂。 [0037] The sixth step, cooled to 20 ° C, 30% sodium hydroxide solution adjusted to pH 5.0, the mass fraction of the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.

[0038] 实施例二 [0038] Second Embodiment

[0039] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,具体包括以下步骤: [0039] A method for preparing reactive surface sizing agent benzenepropanoic soap emulsifier-free, includes the following steps:

[0040] 第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在81 °C时反应1. 6 小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 1小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5, [0040] The first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor in the reactor at 81 ° C 1. 6 hours together with 2.5 g of maleic anhydride the reaction incubation was continued for 1.1 hours, to give maleic acid, polyethylene glycol monostearate, polyethylene glycol-400 of said mass stearic acid and maleic anhydride in the ratio of 10: 7: 2.5

[0041] 第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体, [0041] The second step, 25 g of maleic acid and polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing,

[0042] 第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, [0042] The third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared,

[0043] 第四步,在第二反应器中加入124克去离子水,升温至62°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : 40,整个加料时间为1.2小时, [0043] The fourth step, in the second reactor was added 124 grams of deionized water, warmed to 62 ° C, deionized water and the mass ratio of the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution 40 g monomer mixture, an aqueous solution of ammonium persulfate and monomer mixture mass ratio of 21: 40, the entire addition time was 1.2 hours

[0044] 第五步,加料完毕后于82°C保温反应2. 2小时, [0044] The fifth step, after the addition was complete the reaction was kept 82 ° C 2.2 hours,

[0045] 第六步,降温到22°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 4,出料, 得到反应型乳化剂无皂苯丙表面施胶剂。 [0045] The sixth step, cooled to 22 ° C, 30% sodium hydroxide solution adjusted to pH 5.4, the mass fraction of the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.

[0046] 实施例三 [0046] Example three

[0047] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,具体包括以下步骤: [0047] A method for preparing reactive surface sizing agent benzenepropanoic soap emulsifier-free, includes the following steps:

[0048] 第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在82°C时反应1. 7 小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 2小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5, [0048] The first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor in the reactor at 82 ° C 1. 7 hours coupled with 2.5 g of maleic anhydride the reaction incubation was continued for 1.2 hours, to give maleic acid, polyethylene glycol monostearate, polyethylene glycol-400 of said mass stearic acid and maleic anhydride in the ratio of 10: 7: 2.5

[0049] 第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体, [0049] The second step, 25 g of maleic acid and polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing,

7[0050] 第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, 7 [0050] The third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared,

[0051] 第四步,在第二反应器中加入124克去离子水,升温至64°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : 40,整个加料时间为1.4小时, [0051] The fourth step, in the second reactor was added 124 grams of deionized water, warmed to 64 ° C, deionized water and the mass ratio of the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution 40 g monomer mixture, an aqueous solution of ammonium persulfate and monomer mixture mass ratio of 21: 40, the entire addition time was 1.4 hours,

[0052] 第五步,加料完毕后于84°C保温反应2. 4小时, [0052] The fifth step of 84 ° C after the addition was complete the reaction was kept 2.4 hours,

[0053] 第六步,降温到24°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 8,出料, 得到反应型乳化剂无皂苯丙表面施胶剂。 [0053] The sixth step, cooled to 24 ° C, 30% sodium hydroxide solution adjusted to pH 5.8, the mass fraction of the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.

[0054] 实施例四 [0054] Fourth Embodiment

[0055] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,具体包括以下步骤: [0055] A method for preparing reactive surface sizing agent benzenepropanoic soap emulsifier-free, includes the following steps:

[0056] 第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在83°C时反应1. 8 小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 3小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5, [0056] The first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor in the reactor at 83 ° C 1. 8 hours together with 2.5 g of maleic anhydride the reaction incubation was continued for 1.3 hours, to give maleic acid, polyethylene glycol monostearate, polyethylene glycol-400 of said mass stearic acid and maleic anhydride in the ratio of 10: 7: 2.5

[0057] 第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体, [0057] The second step, 25 g of maleic acid and polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing,

[0058] 第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, [0058] The third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared,

[0059] 第四步,在第二反应器中加入124克去离子水,升温至66°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : 40,整个加料时间为1.6小时, [0059] The fourth step, in the second reactor was added 124 grams of deionized water, warmed to 66 ° C, deionized water and the mass ratio of the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution 40 g monomer mixture, an aqueous solution of ammonium persulfate and monomer mixture mass ratio of 21: 40, the entire addition time was 1.6 hours,

[0060] 第五步,加料完毕后于86°C保温反应2. 6小时, [0060] The fifth step, after the addition was complete the reaction was kept 86 ° C 2.6 hours,

[0061] 第六步,降温到26°C,用质量分数为30%的氢氧化钠溶液调节pH值为6. 2,出料, 得到反应型乳化剂无皂苯丙表面施胶剂。 [0061] The sixth step, cooled to 26 ° C, 30% sodium hydroxide solution adjusted to pH 6.2, the mass fraction of the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.

[0062] 实施例五 [0062] Embodiment V

[0063] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,具体包括以下步骤: [0063] A method for preparing reactive surface sizing agent benzenepropanoic soap emulsifier-free, includes the following steps:

[0064] 第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在84°C时反应1. 9 小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 4小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5, [0064] The first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor in the reactor at 84 ° C 1. 9 hour, plus 2.5 g of maleic anhydride the reaction incubation was continued for 1.4 hours, to give maleic acid, polyethylene glycol monostearate, polyethylene glycol-400 of said mass stearic acid and maleic anhydride in the ratio of 10: 7: 2.5

[0065] 第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体, [0065] The second step, 25 g of maleic acid and polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing,

[0066] 第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, [0066] The third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared,

[0067] 第四步,在第二反应器中加入124克去离子水,升温至68°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : 40,整个加料时间为1.8小时, [0067] The fourth step, in the second reactor was added 124 grams of deionized water, warmed to 68 ° C, deionized water and the mass ratio of the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution 40 g monomer mixture, an aqueous solution of ammonium persulfate and monomer mixture mass ratio of 21: 40, the entire addition time was 1.8 hours.

[0068] 第五步,加料完毕后于88°C保温反应2. 8小时, [0068] The fifth step, after the addition was complete the reaction was kept 88 ° C 2.8 hours,

[0069] 第六步,降温到28°C,用质量分数为30%的氢氧化钠溶液调节pH值为6. 6,出料, 得到反应型乳化剂无皂苯丙表面施胶剂。 [0069] The sixth step, cooled to 28 ° C, 30% sodium hydroxide solution adjusted to pH 6.6, the mass fraction of the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.

[0070] 实施例六 [0070] Sixth Embodiment

[0071] 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,具体包括以下步骤: [0071] A method for preparing reactive surface sizing agent benzenepropanoic soap emulsifier-free, includes the following steps:

[0072] 第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在85°C时反应2. 0 小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 5小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5, [0072] The first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor in the reactor at 85 ° C 2. 0 hour, plus 2.5 g of maleic anhydride the reaction incubation was continued for 1.5 hours, to give maleic acid, polyethylene glycol monostearate, polyethylene glycol-400 of said mass stearic acid and maleic anhydride in the ratio of 10: 7: 2.5

[0073] 第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体, [0073] The second step, 25 g of maleic acid and polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing,

[0074] 第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, [0074] The third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared,

[0075] 第四步,在第二反应器中加入124克去离子水,升温至70°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : 40,整个加料时间为2小时, [0075] The fourth step, in the second reactor was added 124 grams of deionized water, warmed to 70 ° C, deionized water and the mass ratio of the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution 40 g monomer mixture, an aqueous solution of ammonium persulfate and monomer mixture mass ratio of 21: 40, the entire addition time was 2 hours.

[0076] 第五步,加料完毕后于90°C保温反应3. 0小时, [0076] The fifth step, the addition was complete the reaction was kept 90 ° C after 3.0 hours,

[0077] 第六步,降温到30°C,用质量分数为30%的氢氧化钠溶液调节pH值为7. 0,出料, 得到反应型乳化剂无皂苯丙表面施胶剂。 [0077] The sixth step, cooled to 30 ° C, 30% sodium hydroxide solution adjusted to pH 7.0, the mass fraction of the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.

Claims (9)

  1. 一种反应型乳化剂无皂苯丙表面施胶剂,其特征在于:一种反应型乳化剂无皂苯丙表面施胶剂的分子结构为:反应型乳化剂无皂苯丙表面施胶剂其中x、y、z、m、n均为大于零的整数。 A reactive emulsifier free styrene - acrylate surface sizing agent, characterized in that: a reactive emulsifier free styrene - acrylate surface sizing agent of the molecular structure: Reactive Emulsifier free styrene - acrylate surface sizing agent wherein x, y, z, m, n are integers greater than zero. FDA0000021243390000011.tif FDA0000021243390000011.tif
  2. 2. 一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:先由聚乙二醇、 硬脂酸和顺丁烯二酸酐反应得到顺丁烯二酸聚乙二醇单硬酯酸酯,再以过硫酸铵为引发剂,由顺丁烯二酸聚乙二醇单硬脂酸酯与苯乙烯、丙烯酰胺、丙烯酸和丙烯腈通过共聚合反应制备反应型乳化剂无皂苯丙表面施胶剂。 A method for preparing non-reactive emulsifier soap benzenepropanoic surface sizing agent, characterized in that: first polyethylene glycol, stearic acid and maleic anhydride obtained by reacting maleic acid polyethylene glycol monostearate, and then ammonium persulfate as the initiator, a maleic acid polyethylene glycol monostearate and styrene, acrylamide, acrylic acid and acrylonitrile prepared by the copolymerization reaction of reactive emulsifier free styrene - acrylate surface sizing agent.
  3. 3.根据权利要求2所述的一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:具体包括以下步骤:第一步,将聚乙二醇-400和硬脂酸加入第一反应器中在80-85°C时反应1. 5-2. 0小时, 再加入顺丁烯二酸酐继续保温反应1. 0-1. 5小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯, 所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5,第二步,将顺丁烯二酸聚乙二醇单硬脂酸酯、苯乙烯、丙烯酰胺、丙烯酸和丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体,第三步,将过硫酸铵和去离子水以质量比1 : 20制成过硫酸铵水溶液, 第四步,在第二反应器中加入去离子水,升温至60-70°C,去离子水和所制混合单体的质量比为124 : 40,再加入过硫酸铵水溶液和所制混合单体,过硫酸铵水溶液与所制混合单体的质量比为21 : 40,整个加料时 3. A member according to claim 2, wherein the reactive emulsifier-free preparation of styrene - acrylate surface sizing agent, characterized in that: includes the following steps: the first step, and stearyl polyethylene glycol-400 acid added to the first reactor in the reactor 1. 5-2. 0 hours at 80-85 ° C, maleic anhydride was added the reaction was continued incubation 1. 0-1. 5 hours to obtain poly maleic acid ethylene glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5, the second step, the maleic acid polyethylene glycol alcohol monostearate, styrene, acrylamide, acrylic acid and acrylonitrile by 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing the third step, ammonium persulfate and deionized water mass ratio of 1: 20 ammonium persulfate aqueous solution prepared, a fourth step of deionized water was added in the second reactor and heated to 60-70 ° C, mass of deionized water and the mixing ratio of the monomers prepared was 124: 40, throughout the addition: 40, was added and the aqueous ammonium persulfate solution prepared monomer mixture of ammonium persulfate and an aqueous solution of monomer mixture mass ratio of 21 prepared 为1-2小时,第五步,加料完毕后于80-90°C保温反应2. 0-3. 0小时,第六步,降温到20-30°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 0-7. 0,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 1-2 hours, the fifth step, after the addition was complete the reaction was kept 80-90 ° C 2. 0-3. 0 hours, a sixth step, cooled to 20-30 ° C, with a mass fraction of 30% hydrogen sodium hydroxide solution was adjusted to pH 5. 0-7. 0, the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.
  4. 4.根据权利要求2或3所述的一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:具体包括以下步骤:第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在80°C时反应1. 5小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 0小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5,第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体,第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, 第四步,在第二反应器中加入124克去离子水,升温至60°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为2 A reactive type according to claim 2 or 3, wherein said emulsifier-free preparation of styrene - acrylate surface sizing agent, characterized in that: includes the following steps: a first step, 10 g of polyethylene glycol - 400 and 7 grams of stearic acid is added first into the reactor for 1.5 hours at 80 ° C, combined with 2.5 g of maleic anhydride, reaction was further incubated for 1.0 hours, to obtain poly maleic acid ethylene glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5, the second step, 25 g of maleic acid, poly ethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing the third step , 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared, a fourth step, 124 g of deionized water was added in the second reactor, the temperature was raised to 60 ° C, to mass ratio of DI water and the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution and 40 g monomer mixture, aqueous ammonium persulfate solution mass ratio of the monomer mixture is 2 1 : 40,整个加料时间为1小时, 第五步,加料完毕后于80°C保温反应2. 0小时,第六步,降温到20°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 0,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 1:40, throughout the addition time of 1 hour, the fifth step, after the addition was complete the reaction was kept 80 ° C 2.0 hours, a sixth step, cooled to 20 ° C, with a mass fraction of 30% sodium hydroxide solution adjusted to pH 5.0, the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.
  5. 5.根据权利要求2或3所述的一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:具体包括以下步骤:第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在81°C时反应1. 6小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 1小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5,第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体,第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, 第四步,在第二反应器中加入124克去离子水,升温至62°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为2 A reactive claim 2 or claim 3 emulsifier-free preparation of styrene - acrylate surface sizing agent, characterized in that: includes the following steps: a first step, 10 g of polyethylene glycol - 400 and 7 grams of stearic acid is added first into the reactor for 1.6 hours at 81 ° C, combined with 2.5 g of maleic anhydride incubation was continued for 1.1 hours the reaction, maleic acid to give poly ethylene glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5, the second step, 25 g of maleic acid, poly ethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing the third step , 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared, a fourth step, was added 124 g of deionized water in a second reactor and heated to 62 ° C, to mass ratio of DI water and the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution and 40 g monomer mixture, aqueous ammonium persulfate solution mass ratio of the monomer mixture is 2 1 : 40,整个加料时间为1.2小时, 第五步,加料完毕后于82°C保温反应2. 2小时,第六步,降温到22°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 4,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 1:40, the entire addition time was 1.2 hours, the fifth step, the addition was complete the reaction was kept 82 ° C after 2.2 hours, a sixth step, cooled to 22 ° C, with a mass fraction of 30% sodium hydroxide solution adjusted to pH 5.4, the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.
  6. 6.权利要求2或3所述的一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:具体包括以下步骤:第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在82°C时反应1. 7小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 2小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5,第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体,第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, 第四步,在第二反应器中加入124克去离子水,升温至64°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : One reaction type 2 or claim 3, emulsifier-free preparation of styrene - acrylate surface sizing agent, characterized in that: includes the following steps: a first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor for 1.7 hours at 82 ° C, combined with 2.5 g of maleic anhydride incubation was continued for 1.2 hours the reaction, polyethylene maleic acid to give glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5, the second step, 25 g of maleic acid polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing the third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared, a fourth step, was added 124 g of deionized water in a second reactor and heated to 64 ° C, deionized mass ratio of water and the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution and 40 g of the monomer mixture and the aqueous ammonium persulfate solution mass ratio of monomer mixture 21: 40,整个加料时间为1.4小时, 第五步,加料完毕后于84°C保温反应2. 4小时,第六步,降温到24°C,用质量分数为30%的氢氧化钠溶液调节pH值为5. 8,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 40, the entire addition time was 1.4 hours, the fifth step, the addition was complete the reaction was kept 84 ° C after 2.4 hours, a sixth step, cooled to 24 ° C, with a mass fraction of 30% sodium hydroxide solution to adjust pH value of 5.8, the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.
  7. 7.权利要求2或3所述的一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:具体包括以下步骤:第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在83°C时反应1. 8小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 3小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5,第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体,第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, 第四步,在第二反应器中加入124克去离子水,升温至66°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为21 : One reaction type 2 or claim 3, emulsifier-free preparation of styrene - acrylate surface sizing agent, characterized in that: includes the following steps: a first step, 10 g of polyethylene glycol-400 and 7 grams of stearic acid added to the first reactor for 1.8 hours at 83 ° C, combined with 2.5 g of maleic anhydride incubation was continued for 1.3 hours the reaction, polyethylene maleic acid to give glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5, the second step, 25 g of maleic acid polyethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing the third step, 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared, a fourth step, was added 124 g of deionized water in a second reactor and heated to 66 ° C, deionized mass ratio of water and the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution and 40 g of the monomer mixture and the aqueous ammonium persulfate solution mass ratio of monomer mixture 21: 40,整个加料时间为1.6小时, 第五步,加料完毕后于86°C保温反应2. 6小时,第六步,降温到26°C,用质量分数为30%的氢氧化钠溶液调节pH值为6. 2,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 40, the entire addition time was 1.6 hours, the fifth step, the addition was complete the reaction was kept 86 ° C after 2.6 hours, a sixth step, cooled to 26 ° C, with a mass fraction of 30% sodium hydroxide solution to adjust pH value of 6.2, the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.
  8. 8.根据权利要求2或3所述的一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:具体包括以下步骤:第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在84°C时反应1. 9小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 4小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5,第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体,第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, 第四步,在第二反应器中加入124克去离子水,升温至68°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为2 A reactive type according to claim 2 or 3, wherein said emulsifier-free preparation of styrene - acrylate surface sizing agent, characterized in that: includes the following steps: a first step, 10 g of polyethylene glycol - 400 and 7 grams of stearic acid is added first into the reactor for 1.9 hours at 84 ° C, combined with 2.5 g of maleic anhydride reaction was further incubated for 1.4 hours, to obtain poly maleic acid ethylene glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5, the second step, 25 g of maleic acid, poly ethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing the third step , 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared, a fourth step, was added 124 g of deionized water in a second reactor and heated to 68 ° C, to mass ratio of DI water and the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution and 40 g monomer mixture, aqueous ammonium persulfate solution mass ratio of the monomer mixture is 2 1 : 40,整个加料时间为1.8小时, 第五步,加料完毕后于88°C保温反应2. 8小时,第六步,降温到28°C,用质量分数为30%的氢氧化钠溶液调节pH值为6. 6,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 1:40, throughout the addition time was 1.8 hours, the fifth step, the addition was complete the reaction was kept 88 ° C after 2.8 hours, a sixth step, cooled to 28 ° C, with a mass fraction of 30% sodium hydroxide solution adjust the pH to 6.6, the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.
  9. 9.根据权利要求2或3所述的一种反应型乳化剂无皂苯丙表面施胶剂的制备方法,其特征在于:具体包括以下步骤:第一步,将10克聚乙二醇-400和7克硬脂酸加入第一反应器中在85°C时反应2. 0小时,再加2. 5克顺丁烯二酸酐继续保温反应1. 5小时,得到顺丁烯二酸聚乙二醇单硬脂酸酯,所说的聚乙二醇-400、硬酯酸和顺丁烯二酸酐的质量比为10 : 7 : 2.5,第二步,将25克顺丁烯二酸聚乙二醇单硬脂酸酯、5克苯乙烯、6克丙烯酰胺、3克丙烯酸和1克丙烯腈按25 : 5 : 6 : 3 : 1的质量比混合制成混合单体,第三步,将1克过硫酸铵和20克去离子水以质量比1 : 20制成过硫酸铵水溶液, 第四步,在第二反应器中加入124克去离子水,升温至70°C,去离子水和混合单体的质量比为124 : 40,再加入21克过硫酸铵水溶液和40克混合单体,过硫酸铵水溶液与混合单体的质量比为2 A reactive type according to claim 2 or 3, wherein said emulsifier-free preparation of styrene - acrylate surface sizing agent, characterized in that: includes the following steps: a first step, 10 g of polyethylene glycol - 400 and 7 grams of stearic acid is added first into the reactor for 2.0 hours at 85 ° C, combined with 2.5 g of maleic anhydride, reaction was further incubated for 1.5 hours, to obtain poly maleic acid ethylene glycol monostearate, polyethylene glycol-400 of said mass ratio of stearic acid and maleic anhydride is 10: 7: 2.5, the second step, 25 g of maleic acid, poly ethylene glycol monostearate, 5 g of styrene, 6 g of acrylamide, 3 g of acrylic acid and 1 g of acrylonitrile of 25: 5: 6: 3: 1 mass ratio of monomer mixture prepared by mixing the third step , 1 g of ammonium persulfate and 20 g deionized water to mass ratio of 1: 20 ammonium persulfate aqueous solution prepared, a fourth step, was added 124 g of deionized water in a second reactor and heated to 70 ° C, to mass ratio of DI water and the monomer mixture is 124: 40, then 21 grams of ammonium persulfate aqueous solution and 40 g monomer mixture, aqueous ammonium persulfate solution mass ratio of the monomer mixture is 2 1 : 40,整个加料时间为2小时, 第五步,加料完毕后于90°C保温反应3. 0小时,第六步,降温到30°C,用质量分数为30%的氢氧化钠溶液调节pH值为7. 0,出料,得到反应型乳化剂无皂苯丙表面施胶剂。 1:40, throughout the addition time was 2 hours, the fifth step, the addition was complete the reaction was kept 90 ° C after 3.0 hours, a sixth step, cooled to 30 ° C, with a mass fraction of 30% sodium hydroxide solution adjusted to pH 7.0, the material, to obtain a reaction emulsifier free styrene - acrylate surface sizing agent.
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