技术领域technical field
本发明属于高分子化学施胶剂技术领域，特别涉及一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法。The invention belongs to the technical field of polymer chemical sizing agents, in particular to a preparation method of cationic sweet potato starch AKD medium/alkaline sizing agent.
背景技术Background technique
现代施胶技术的重大进步是中/碱性施胶技术的推广，酸性造纸转化为中/碱性造纸是世界造纸史上的一大变革。中/碱性施胶是在造纸工艺过程中，将pH值调节到7以上，原则上不用硫酸铝的一种施胶方法。常用的中/碱性施胶剂烷基烯酮二聚体（简称AKD）是20世纪40年代末期研究开发的产品，AKD是一种可与纤维素反应的反应型中/碱性施胶剂，它既能作为浆内施胶剂，又能作为表面施胶剂。其结构特点是由活性基团和疏水基团构成，AKD的熔点较低，在纸机干燥部的高温条件下分子中的活性基团四元内酯环能和纤维素上的羟基反应形成β-酮基酯键并定位在纤维上，疏水性基团长链烷基在纤维表面产生抗水作用。通过AKD中/碱性施胶，纸张白度、手感、抗水性、物理强度、印刷适性、耐老化性和填料的单程留着率等都有明显提高。而且可以采用廉价的重质碳酸钙为填料，减少了白水中有害物质的含量，提高了白水的循环利用率，同时AKD比酸性施胶剂的成本低。采用AKD进行中/碱性施胶能够提高纸品质量和售价、降低能耗、改善环境污染和纸机运行性能等，可取得明显的经济效益和社会效益，因此越来越多的造纸企业认识到使用AKD中/碱性施胶剂的优越性和必要性。我国造纸原料以草浆为主，木材资源短缺，二次纤维用量增多，运用中/碱性施胶技术具有现实意义。伴随AKD中/碱性施胶技术在我国应用领域逐步扩大，工艺技术日益成熟，中/碱性造纸的效益逐步得到体现，加快了造纸工业由酸性造纸向中/碱性造纸转变的趋势，近年来AKD已成为国内纸厂使用最多、最成熟、最有效的中/碱性施胶剂。The major progress of modern sizing technology is the promotion of medium/alkaline sizing technology. The conversion of acidic papermaking to medium/alkaline papermaking is a major change in the history of papermaking in the world. Medium/alkaline sizing is a sizing method that adjusts the pH value to above 7 during the papermaking process and does not use aluminum sulfate in principle. The commonly used medium/alkaline sizing agent alkyl ketene dimer (AKD for short) is a product researched and developed in the late 1940s. AKD is a reactive medium/alkaline sizing agent that can react with cellulose , it can be used as both internal sizing agent and surface sizing agent. Its structural characteristics are composed of active groups and hydrophobic groups. The melting point of AKD is low. Under the high temperature conditions of the paper machine drying section, the active group in the molecule can react with the hydroxyl group on the cellulose to form β - The keto ester bond is positioned on the fiber, and the long-chain alkyl group of the hydrophobic group produces a water-resistant effect on the surface of the fiber. Through AKD medium/alkaline sizing, paper whiteness, hand feeling, water resistance, physical strength, printability, aging resistance and single-pass retention rate of fillers have all been significantly improved. Moreover, cheap heavy calcium carbonate can be used as filler, which reduces the content of harmful substances in white water and improves the recycling rate of white water. At the same time, the cost of AKD is lower than that of acid sizing agent. The use of AKD for medium/alkaline sizing can improve the quality and selling price of paper products, reduce energy consumption, improve environmental pollution and paper machine operation performance, etc., and can achieve obvious economic and social benefits. Therefore, more and more papermaking enterprises Recognize the superiority and necessity of using AKD medium/alkaline sizing agent. In my country, straw pulp is the main raw material for papermaking, wood resources are in short supply, and the amount of secondary fiber is increasing. It is of practical significance to use medium/alkaline sizing technology. With the gradual expansion of the application field of AKD medium/alkaline sizing technology in my country, the process technology has become increasingly mature, and the benefits of medium/alkaline papermaking have been gradually reflected, which has accelerated the trend of the paper industry from acidic papermaking to medium/alkaline papermaking. In recent years, AKD has become the most mature and effective medium/alkaline sizing agent used by domestic paper mills.
AKD中/碱性施胶赋予纸张一些优异性能，同时也有其不足之处。传统AKD乳液采用木薯阳离子淀粉作为AKD的乳化剂，木薯淀粉纯度高，糊化温度低，糊液流动性好，透明度高、凝沉性弱，不易分层。但其价格较高，由此制得的AKD乳液价格较高，市场竞争力差。近年来提高和完善AKD乳液性能的研究日趋活跃，提高AKD的市场竞争力，开发和生产性能优异、价格便宜的AKD中/碱性施胶是我国造纸科研工作者一直努力研究的课题。AKD medium/alkaline sizing endows paper with some excellent properties, but also has its disadvantages. Traditional AKD emulsion uses tapioca cationic starch as the emulsifier of AKD. Tapioca starch has high purity, low gelatinization temperature, good fluidity of paste liquid, high transparency, weak retrogradation, and is not easy to layer. But its price is higher, the AKD emulsion price that makes thus is higher, and market competitiveness is poor. In recent years, the research on improving and perfecting the performance of AKD emulsion has become increasingly active. Improving the market competitiveness of AKD, developing and producing AKD medium/alkaline sizing with excellent performance and low price are the subjects that Chinese paper researchers have been working hard on.
发明内容Contents of the invention
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阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，所得的中/碱性施胶剂具有很好的稳定性，能够提高纸张的施胶度和表面强度，并且降低了施胶成本。In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of cationic sweet potato starch AKD middle/alkaline sizing agent, the middle/alkaline sizing agent of gained has good stability, can improve The sizing degree and surface strength of the paper are improved, and the sizing cost is reduced.
为达到上述目的，本发明采用的技术方案为：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，包括以下步骤：A kind of preparation method of cationic sweet potato starch AKD/alkaline sizing agent, comprises the following steps:
第一步，将水、红薯淀粉和真菌α-淀粉酶加入第一反应器中在50-55℃时反应1.0-2.0小时，得到降解红薯淀粉，水、红薯淀粉和真菌α-淀粉酶的质量比为200∶100∶0.6，然后向第一反应器中加入氢氧化钠，升温到60-70℃加入3-氯-2-羟丙基三甲基氯化铵，再升温至90-95℃反应1-2小时，降温至50-55℃加入醋酸，再降至20-30℃，红薯淀粉、氢氧化钠、3-氯-2-羟丙基三甲基氯化铵和醋酸的质量比为100∶7∶49∶5，In the first step, water, sweet potato starch and fungal α-amylase are added to the first reactor and reacted for 1.0-2.0 hours at 50-55°C to obtain the quality of degraded sweet potato starch, water, sweet potato starch and fungal α-amylase The ratio is 200:100:0.6, then add sodium hydroxide to the first reactor, raise the temperature to 60-70°C, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, and then raise the temperature to 90-95°C React for 1-2 hours, lower the temperature to 50-55°C and add acetic acid, then lower to 20-30°C, the mass ratio of sweet potato starch, sodium hydroxide, 3-chloro-2-hydroxypropyltrimethylammonium chloride and acetic acid is 100:7:49:5,
第二步，向第一反应器中加水，调节体系固含量至20-25%，即得阳离子红薯淀粉乳化剂，In the second step, add water to the first reactor to adjust the solid content of the system to 20-25%, to obtain a cationic sweet potato starch emulsifier,
第三步，在第二反应器中加入阳离子红薯淀粉乳化剂、石蜡和AKD，其中阳离子红薯淀粉乳化剂、石蜡和AKD的质量比为110∶110∶120，升高温度至70-75℃，待石蜡和AKD熔融后，搅拌30-40分钟，在搅拌下加入75-80℃的热水分散调节至固含量至15-20%，制得阳离子红薯淀粉AKD亚稳定乳液，将亚稳定乳液经20-30MPa均质后，冷却至25-30℃，得到固含量为15-20%的稳定的阳离子红薯淀粉AKD中/碱性施胶剂，所述的石蜡为半精炼石蜡或精炼石蜡，或两者以任意比例的混合物。The 3rd step, in the second reactor, add cationic sweet potato starch emulsifier, paraffin and AKD, wherein the mass ratio of cationic sweet potato starch emulsifier, paraffin and AKD is 110: 110: 120, raising temperature to 70-75 ℃, After the paraffin and AKD are melted, stir for 30-40 minutes, add hot water at 75-80°C to disperse and adjust the solid content to 15-20% under stirring, and prepare the cationic sweet potato starch AKD metastable emulsion, and pass the metastable emulsion through After homogenizing at 20-30MPa, cool to 25-30°C to obtain a stable cationic sweet potato starch AKD medium/alkaline sizing agent with a solid content of 15-20%, and the paraffin wax is semi-refined paraffin wax or refined paraffin wax, or A mixture of the two in any proportion.
将此阳离子红薯淀粉AKD中/碱性施胶剂用于以100%国内废纸抄造的110克/米2瓦楞原纸中，淀粉用量65-70千克/吨纸，阳离子红薯淀粉AKD中/碱性施胶剂2.5-3.0千克/吨纸，表面施胶剂后瓦楞原纸的Cobb值为35-40克/米2，环压指数为8.0-8.5牛·米2/克,裂断长为4.5-5.0千米，达到A级高强瓦楞原纸质量标准，用阳离子红薯淀粉AKD中/碱性施胶剂施胶后，每吨瓦楞原纸的施胶成本降低了4-9元。The cationic sweet potato starch AKD medium/alkaline sizing agent is used in 110 g/m2 corrugated base paper made of 100% domestic waste paper, the amount of starch is 65-70 kg/ton of paper, and the cationic sweet potato starch AKD medium/alkaline The sizing agent is 2.5-3.0 kg/ton paper, the Cobb value of the corrugated base paper after the surface sizing agent is 35-40 g/m2 , the ring pressure index is 8.0-8.5 N·m2 /g, and the breaking length is 4.5- 5.0 kilometers, reaching the quality standard of A-grade high-strength corrugated base paper. After sizing with cationic sweet potato starch AKD medium/alkaline sizing agent, the sizing cost per ton of corrugated base paper is reduced by 4-9 yuan.
本发明制备过程中不使用小分子表面活性剂，有利于环境保护和应用效果的提高。先将红薯淀粉降解然后进行阳离子化，将其作为乳化剂应用于石蜡和AKD的乳化，制备的中/碱性施胶剂乳液粘度小，稳定性好。制备的乳液颗粒带阳电荷，有助于留着并且与带负电荷的纸张纤维能够紧密结合，不但提高乳液稳定性能和施胶性能，并且降低了施胶成本。The preparation process of the present invention does not use a small molecule surfactant, which is beneficial to environmental protection and improvement of application effect. The sweet potato starch was firstly degraded and then cationized. It was used as an emulsifier in the emulsification of paraffin and AKD. The prepared medium/alkaline sizing agent emulsion had low viscosity and good stability. The prepared emulsion particles are positively charged, which is helpful for retention and can be tightly combined with negatively charged paper fibers, which not only improves the emulsion stability and sizing performance, but also reduces the sizing cost.
具体实施方式Detailed ways
下面将以具体实施例对本发明作进一步详细的描述。The present invention will be further described in detail with specific examples below.
实施例一Embodiment one
一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，包括以下步骤：A kind of preparation method of cationic sweet potato starch AKD/alkaline sizing agent, comprises the following steps:
第一步，将200克水、100克红薯淀粉和0.6克真菌α-淀粉酶加入第一反应器中在50℃时反应1.0小时，得到降解红薯淀粉，水、红薯淀粉和真菌α-淀粉酶的质量比为200∶100∶0.6，然后向第一反应器中加入7克氢氧化钠，升温到60℃加入49克3-氯-2-羟丙基三甲基氯化铵，再升温至90℃反应2小时，降温至50℃加入5克醋酸，再降至20℃，红薯淀粉、氢氧化钠、3-氯-2-羟丙基三甲基氯化铵和醋酸的质量比为100∶7∶49∶5，In the first step, 200 grams of water, 100 grams of sweet potato starch and 0.6 grams of fungal α-amylase are added to the first reactor and reacted for 1.0 hour at 50 ° C to obtain degraded sweet potato starch, water, sweet potato starch and fungal α-amylase The mass ratio is 200: 100: 0.6, then 7 grams of sodium hydroxide are added to the first reactor, and the temperature is raised to 60°C to add 49 grams of 3-chloro-2-hydroxypropyl trimethylammonium chloride, and then the temperature is raised to React at 90°C for 2 hours, cool down to 50°C and add 5 grams of acetic acid, then lower to 20°C, the mass ratio of sweet potato starch, sodium hydroxide, 3-chloro-2-hydroxypropyltrimethylammonium chloride and acetic acid is 100 :7:49:5,
第二步，向第一反应器中加水，调节体系固含量至20%，即得阳离子红薯淀粉乳化剂，In the second step, add water to the first reactor to adjust the solid content of the system to 20%, to obtain a cationic sweet potato starch emulsifier,
第三步，在第二反应器中加入110克阳离子红薯淀粉乳化剂、110克石蜡和120克AKD，其中阳离子红薯淀粉乳化剂、石蜡和AKD的质量比为110∶110∶120，升高温度至70℃，待石蜡和AKD熔融后，搅拌40分钟，在搅拌下加入75℃的热水分散调节至固含量至15%，制得阳离子红薯淀粉AKD亚稳定乳液，将亚稳定乳液经20MPa均质后，冷却至25℃，得到固含量为15%的稳定的阳离子红薯淀粉AKD中/碱性施胶剂，所述的石蜡为半精炼石蜡。The 3rd step, in the second reactor, add 110 gram cationic sweet potato starch emulsifiers, 110 gram paraffin and 120 gram AKD, wherein the mass ratio of cationic sweet potato starch emulsifiers, paraffin and AKD is 110: 110: 120, raising temperature to 70°C, after the paraffin and AKD are melted, stir for 40 minutes, add hot water at 75°C under stirring to disperse and adjust the solid content to 15%, and obtain a cationic sweet potato starch AKD metastable emulsion, and put the metastable emulsion through 20MPa homogenization After massaging, cool to 25°C to obtain a stable cationic sweet potato starch AKD medium/alkaline sizing agent with a solid content of 15%, and the paraffin wax is semi-refined paraffin wax.
将此阳离子红薯淀粉AKD中/碱性施胶剂用于以100%国内废纸抄造的110克/米2瓦楞原纸中，淀粉用量65千克/吨纸，阳离子红薯淀粉AKD中/碱性施胶剂2.5千克/吨纸，表面施胶剂后瓦楞原纸的Cobb值为40克/米2，环压指数为8.0牛·米2/克,裂断长为4.5千米，达到A级高强瓦楞原纸质量标准，用阳离子红薯淀粉AKD中/碱性施胶剂施胶后，每吨瓦楞原纸的施胶成本降低了9元。Use this cationic sweet potato starch AKD medium/alkaline sizing agent for 110 g/m2 corrugated base paper made from 100% domestic waste paper, the amount of starch is 65 kg/ton of paper, cationic sweet potato starch AKD medium/alkaline sizing 2.5 kg/ton of paper, the Cobb value of the corrugated base paper after surface sizing is 40 g/m2 , the ring pressure index is 8.0 N·m2 /g, and the breaking length is 4.5 km, reaching A-grade high-strength corrugated base paper Quality standard, after sizing with cationic sweet potato starch AKD medium/alkaline sizing agent, the sizing cost per ton of corrugated base paper is reduced by 9 yuan.
实施例二Embodiment two
一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，包括以下步骤：A kind of preparation method of cationic sweet potato starch AKD/alkaline sizing agent, comprises the following steps:
第一步，将200克水、100克红薯淀粉和0.6克真菌α-淀粉酶加入第一反应器中在51℃时反应1.2小时，得到降解红薯淀粉，水、红薯淀粉和真菌α-淀粉酶的质量比为200∶100∶0.6，然后向第一反应器中加入7克氢氧化钠，升温到62℃加入49克3-氯-2-羟丙基三甲基氯化铵，再升温至91℃反应1.8小时，降温至51℃加入5克醋酸，再降至22℃，红薯淀粉、氢氧化钠、3-氯-2-羟丙基三甲基氯化铵和醋酸的质量比为100∶7∶49∶5，In the first step, 200 grams of water, 100 grams of sweet potato starch and 0.6 grams of fungal α-amylase were added to the first reactor and reacted for 1.2 hours at 51 ° C to obtain degraded sweet potato starch, water, sweet potato starch and fungal α-amylase The mass ratio is 200: 100: 0.6, then 7 grams of sodium hydroxide are added to the first reactor, and the temperature is raised to 62° C., 49 grams of 3-chloro-2-hydroxypropyltrimethylammonium chloride is added, and the temperature is raised to React at 91°C for 1.8 hours, cool down to 51°C and add 5 grams of acetic acid, then lower to 22°C, the mass ratio of sweet potato starch, sodium hydroxide, 3-chloro-2-hydroxypropyltrimethylammonium chloride and acetic acid is 100 :7:49:5,
第二步，向第一反应器中加水，调节体系固含量至21%，即得阳离子红薯淀粉乳化剂，In the second step, add water to the first reactor to adjust the solid content of the system to 21%, to obtain a cationic sweet potato starch emulsifier,
第三步，在第二反应器中加入110克阳离子红薯淀粉乳化剂、110克石蜡和120克AKD，其中阳离子红薯淀粉乳化剂、石蜡和AKD的质量比为110∶110∶120，升高温度至71℃，待石蜡和AKD熔融后，搅拌38分钟，在搅拌下加入76℃的热水分散调节至固含量至16%，制得阳离子红薯淀粉AKD亚稳定乳液，将亚稳定乳液经22MPa均质后，冷却至26℃，得到固含量为16%的稳定的阳离子红薯淀粉AKD中/碱性施胶剂，所述的石蜡为精炼石蜡。The 3rd step, in the second reactor, add 110 gram cationic sweet potato starch emulsifiers, 110 gram paraffin and 120 gram AKD, wherein the mass ratio of cationic sweet potato starch emulsifiers, paraffin and AKD is 110: 110: 120, raising temperature to 71°C, after the paraffin and AKD are melted, stir for 38 minutes, add hot water at 76°C under stirring to disperse and adjust the solid content to 16%, and obtain a cationic sweet potato starch AKD metastable emulsion, and put the metastable emulsion through 22MPa homogenization After massaging, it was cooled to 26°C to obtain a stable cationic sweet potato starch AKD medium/alkaline sizing agent with a solid content of 16%, and the paraffin wax was refined paraffin wax.
将此阳离子红薯淀粉AKD中/碱性施胶剂用于以100%国内废纸抄造的110克/米2瓦楞原纸中，淀粉用量66千克/吨纸，阳离子红薯淀粉AKD中/碱性施胶剂2.6千克/吨纸，表面施胶剂后瓦楞原纸的Cobb值为39克/米2，环压指数为8.1牛·米2/克,裂断长为4.6千米，达到A级高强瓦楞原纸质量标准，用阳离子红薯淀粉AKD中/碱性施胶剂施胶后，每吨瓦楞原纸的施胶成本降低了8元。The cationic sweet potato starch AKD medium/alkaline sizing agent is used in 110 g/m2 corrugated base paper made of 100% domestic waste paper, the amount of starch is 66 kg/ton of paper, and the cationic sweet potato starch AKD medium/alkaline sizing 2.6 kg/ton of paper, the Cobb value of the corrugated base paper after surface sizing is 39 g/m2 , the ring pressure index is 8.1 N·m2 /g, and the breaking length is 4.6 km, reaching A-grade high-strength corrugated base paper Quality standard, after sizing with cationic sweet potato starch AKD medium/alkaline sizing agent, the sizing cost per ton of corrugated base paper is reduced by 8 yuan.
实施例三Embodiment three
一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，包括以下步骤：A kind of preparation method of cationic sweet potato starch AKD/alkaline sizing agent, comprises the following steps:
第一步，将200克水、100克红薯淀粉和0.6克真菌α-淀粉酶加入第一反应器中在52℃时反应1.4小时，得到降解红薯淀粉，水、红薯淀粉和真菌α-淀粉酶的质量比为200∶100∶0.6，然后向第一反应器中加入7克氢氧化钠，升温到64℃加入49克3-氯-2-羟丙基三甲基氯化铵，再升温至92℃反应1.6小时，降温至52℃加入5克醋酸，再降至24℃，红薯淀粉、氢氧化钠、3-氯-2-羟丙基三甲基氯化铵和醋酸的质量比为100∶7∶49∶5，In the first step, 200 grams of water, 100 grams of sweet potato starch and 0.6 grams of fungal α-amylase were added to the first reactor and reacted for 1.4 hours at 52°C to obtain degraded sweet potato starch, water, sweet potato starch and fungal α-amylase The mass ratio is 200: 100: 0.6, then 7 grams of sodium hydroxide are added to the first reactor, the temperature is raised to 64 °C, 49 grams of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added, and the temperature is raised to React at 92°C for 1.6 hours, cool down to 52°C and add 5 grams of acetic acid, then lower to 24°C, the mass ratio of sweet potato starch, sodium hydroxide, 3-chloro-2-hydroxypropyltrimethylammonium chloride and acetic acid is 100 :7:49:5,
第二步，向第一反应器中加水，调节体系固含量至22%，即得阳离子红薯淀粉乳化剂，In the second step, water is added to the first reactor to adjust the solid content of the system to 22%, to obtain a cationic sweet potato starch emulsifier,
第三步，在第二反应器中加入110克阳离子红薯淀粉乳化剂、110克石蜡和120克AKD，其中阳离子红薯淀粉乳化剂、石蜡和AKD的质量比为110∶110∶120，升高温度至72℃，待石蜡和AKD熔融后，搅拌36分钟，在搅拌下加入77℃的热水分散调节至固含量至17%，制得阳离子红薯淀粉AKD亚稳定乳液，将亚稳定乳液经24MPa均质后，冷却至27℃，得到固含量为17%的稳定的阳离子红薯淀粉AKD中/碱性施胶剂，所述的石蜡为半精炼石蜡。The 3rd step, in the second reactor, add 110 gram cationic sweet potato starch emulsifiers, 110 gram paraffin and 120 gram AKD, wherein the mass ratio of cationic sweet potato starch emulsifiers, paraffin and AKD is 110: 110: 120, raising temperature to 72°C, after the paraffin and AKD are melted, stir for 36 minutes, add 77°C hot water to disperse and adjust the solid content to 17% under stirring, and prepare the cationic sweet potato starch AKD metastable emulsion, and the metastable emulsion is subjected to 24MPa homogenization After massaging, it was cooled to 27°C to obtain a stable cationic sweet potato starch AKD medium/alkaline sizing agent with a solid content of 17%, and the paraffin wax was semi-refined paraffin wax.
将此阳离子红薯淀粉AKD中/碱性施胶剂用于以100%国内废纸抄造的110克/米2瓦楞原纸中，淀粉用量67千克/吨纸，阳离子红薯淀粉AKD中/碱性施胶剂2.7千克/吨纸，表面施胶剂后瓦楞原纸的Cobb值为38克/米2，环压指数为8.2牛·米2/克,裂断长为4.7千米，达到A级高强瓦楞原纸质量标准，用阳离子红薯淀粉AKD中/碱性施胶剂施胶后，每吨瓦楞原纸的施胶成本降低了7元。Use this cationic sweet potato starch AKD medium/alkaline sizing agent for 110 g/m2 corrugated base paper made of 100% domestic waste paper, the amount of starch is 67 kg/ton of paper, cationic sweet potato starch AKD medium/alkaline sizing 2.7 kg/ton of paper, the Cobb value of the corrugated base paper after surface sizing is 38 g/m2 , the ring pressure index is 8.2 N·m2 /g, and the breaking length is 4.7 km, reaching A-grade high-strength corrugated base paper Quality standard, after sizing with cationic sweet potato starch AKD medium/alkaline sizing agent, the sizing cost per ton of corrugated base paper is reduced by 7 yuan.
实施例四Embodiment Four
一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，包括以下步骤：A kind of preparation method of cationic sweet potato starch AKD/alkaline sizing agent, comprises the following steps:
第一步，将200克水、100克红薯淀粉和0.6克真菌α-淀粉酶加入第一反应器中在53℃时反应1.6小时，得到降解红薯淀粉，水、红薯淀粉和真菌α-淀粉酶的质量比为200∶100∶0.6，然后向第一反应器中加入7克氢氧化钠，升温到66℃加入49克3-氯-2-羟丙基三甲基氯化铵，再升温至93℃反应1.4小时，降温至53℃加入5克醋酸，再降至26℃，红薯淀粉、氢氧化钠、3-氯-2-羟丙基三甲基氯化铵和醋酸的质量比为100∶7∶49∶5，In the first step, 200 grams of water, 100 grams of sweet potato starch and 0.6 grams of fungal α-amylase were added to the first reactor and reacted for 1.6 hours at 53°C to obtain degraded sweet potato starch, water, sweet potato starch and fungal α-amylase The mass ratio is 200: 100: 0.6, then 7 grams of sodium hydroxide are added to the first reactor, and the temperature is raised to 66° C., 49 grams of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added, and the temperature is raised to React at 93°C for 1.4 hours, cool down to 53°C and add 5 grams of acetic acid, then lower to 26°C, the mass ratio of sweet potato starch, sodium hydroxide, 3-chloro-2-hydroxypropyltrimethylammonium chloride and acetic acid is 100 :7:49:5,
第二步，向第一反应器中加水，调节体系固含量至23%，即得阳离子红薯淀粉乳化剂，In the second step, water is added to the first reactor to adjust the solid content of the system to 23%, to obtain a cationic sweet potato starch emulsifier,
第三步，在第二反应器中加入110克阳离子红薯淀粉乳化剂、110克石蜡和120克AKD，其中阳离子红薯淀粉乳化剂、石蜡和AKD的质量比为110∶110∶120，升高温度至73℃，待石蜡和AKD熔融后，搅拌34分钟，在搅拌下加入78℃的热水分散调节至固含量至18%，制得阳离子红薯淀粉AKD亚稳定乳液，将亚稳定乳液经26MPa均质后，冷却至28℃，得到固含量为18%的稳定的阳离子红薯淀粉AKD中/碱性施胶剂，所述的石蜡为精炼石蜡。The 3rd step, in the second reactor, add 110 gram cationic sweet potato starch emulsifiers, 110 gram paraffin and 120 gram AKD, wherein the mass ratio of cationic sweet potato starch emulsifiers, paraffin and AKD is 110: 110: 120, raising temperature to 73°C, after the paraffin and AKD are melted, stir for 34 minutes, add hot water at 78°C under stirring to disperse and adjust the solid content to 18%, and obtain a cationic sweet potato starch AKD metastable emulsion, and the metastable emulsion is subjected to 26MPa homogenization After massaging, it was cooled to 28°C to obtain a stable cationic sweet potato starch AKD medium/alkaline sizing agent with a solid content of 18%, and the paraffin wax was refined paraffin wax.
将此阳离子红薯淀粉AKD中/碱性施胶剂用于以100%国内废纸抄造的110克/米2瓦楞原纸中，淀粉用量68千克/吨纸，阳离子红薯淀粉AKD中/碱性施胶剂2.8千克/吨纸，表面施胶剂后瓦楞原纸的Cobb值为37克/米2，环压指数为8.3牛·米2/克,裂断长为4.8千米，达到A级高强瓦楞原纸质量标准，用阳离子红薯淀粉AKD中/碱性施胶剂施胶后，每吨瓦楞原纸的施胶成本降低了6元。The cationic sweet potato starch AKD medium/alkaline sizing agent is used in 110 g/m2 corrugated base paper made of 100% domestic waste paper, the amount of starch is 68 kg/ton of paper, and the cationic sweet potato starch AKD medium/alkaline sizing 2.8 kg/ton of paper, the Cobb value of the corrugated base paper after the surface sizing agent is 37 g/m2 , the ring pressure index is 8.3 N·m2 /g, and the breaking length is 4.8 km, reaching A-grade high-strength corrugated base paper Quality standard, after sizing with cationic sweet potato starch AKD medium/alkaline sizing agent, the sizing cost per ton of corrugated base paper is reduced by 6 yuan.
实施例五Embodiment five
一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，包括以下步骤：A kind of preparation method of cationic sweet potato starch AKD/alkaline sizing agent, comprises the following steps:
第一步，将200克水、100克红薯淀粉和0.6克真菌α-淀粉酶加入第一反应器中在54℃时反应1.8小时，得到降解红薯淀粉，水、红薯淀粉和真菌α-淀粉酶的质量比为200∶100∶0.6，然后向第一反应器中加入7克氢氧化钠，升温到68℃加入49克3-氯-2-羟丙基三甲基氯化铵，再升温至94℃反应1.2小时，降温至54℃加入5克醋酸，再降至28℃，红薯淀粉、氢氧化钠、3-氯-2-羟丙基三甲基氯化铵和醋酸的质量比为100∶7∶49∶5，In the first step, 200 grams of water, 100 grams of sweet potato starch and 0.6 grams of fungal α-amylase were added to the first reactor and reacted for 1.8 hours at 54 ° C to obtain degraded sweet potato starch, water, sweet potato starch and fungal α-amylase The mass ratio is 200: 100: 0.6, then 7 grams of sodium hydroxide are added to the first reactor, and the temperature is raised to 68° C., 49 grams of 3-chloro-2-hydroxypropyltrimethylammonium chloride is added, and the temperature is raised to React at 94°C for 1.2 hours, cool down to 54°C and add 5 grams of acetic acid, then lower to 28°C, the mass ratio of sweet potato starch, sodium hydroxide, 3-chloro-2-hydroxypropyltrimethylammonium chloride and acetic acid is 100 :7:49:5,
第二步，向第一反应器中加水，调节体系固含量至24%，即得阳离子红薯淀粉乳化剂，In the second step, water is added to the first reactor to adjust the solid content of the system to 24%, to obtain a cationic sweet potato starch emulsifier,
第三步，在第二反应器中加入110克阳离子红薯淀粉乳化剂、110克石蜡和120克AKD，其中阳离子红薯淀粉乳化剂、石蜡和AKD的质量比为110∶110∶120，升高温度至74℃，待石蜡和AKD熔融后，搅拌32分钟，在搅拌下加入79℃的热水分散调节至固含量至19%，制得阳离子红薯淀粉AKD亚稳定乳液，将亚稳定乳液经28MPa均质后，冷却至29℃，得到固含量为19%的稳定的阳离子红薯淀粉AKD中/碱性施胶剂，所述的石蜡为半精炼石蜡和精炼石蜡混合物，两者的质量比为3∶1。The 3rd step, in the second reactor, add 110 gram cationic sweet potato starch emulsifiers, 110 gram paraffin and 120 gram AKD, wherein the mass ratio of cationic sweet potato starch emulsifiers, paraffin and AKD is 110: 110: 120, raising temperature to 74°C, after the paraffin and AKD are melted, stir for 32 minutes, add hot water at 79°C to disperse and adjust the solid content to 19% under stirring, and prepare the cationic sweet potato starch AKD metastable emulsion, and put the metastable emulsion through 28MPa homogenization After qualitative, be cooled to 29 ℃, obtain the stable cationic sweet potato starch AKD medium/alkaline sizing agent that solid content is 19%, described paraffin is semi-refined paraffin and refining paraffin mixture, and the mass ratio of the two is 3: 1.
将此阳离子红薯淀粉AKD中/碱性施胶剂用于以100%国内废纸抄造的110克/米2瓦楞原纸中，淀粉用量69千克/吨纸，阳离子红薯淀粉AKD中/碱性施胶剂2.9千克/吨纸，表面施胶剂后瓦楞原纸的Cobb值为36克/米2，环压指数为8.4牛·米2/克,裂断长为4.9千米，达到A级高强瓦楞原纸质量标准，用阳离子红薯淀粉AKD中/碱性施胶剂施胶后，每吨瓦楞原纸的施胶成本降低了5元。Use this cationic sweet potato starch AKD medium/alkaline sizing agent for 110 g/m2 corrugated base paper made of 100% domestic waste paper, the amount of starch is 69 kg/ton of paper, cationic sweet potato starch AKD medium/alkaline sizing 2.9 kg/ton of paper, the Cobb value of the corrugated base paper after surface sizing is 36 g/m2 , the ring pressure index is 8.4 N·m2 /g, and the breaking length is 4.9 km, reaching A-grade high-strength corrugated base paper Quality standard, after sizing with cationic sweet potato starch AKD medium/alkaline sizing agent, the sizing cost per ton of corrugated base paper is reduced by 5 yuan.
实施例六Embodiment six
一种阳离子红薯淀粉AKD中/碱性施胶剂的制备方法，包括以下步骤：A kind of preparation method of cationic sweet potato starch AKD/alkaline sizing agent, comprises the following steps:
第一步，将200克水、100克红薯淀粉和0.6克真菌α-淀粉酶加入第一反应器中在55℃时反应2.0小时，得到降解红薯淀粉，水、红薯淀粉和真菌α-淀粉酶的质量比为200∶100∶0.6，然后向第一反应器中加入7克氢氧化钠，升温到70℃加入49克3-氯-2-羟丙基三甲基氯化铵，再升温至95℃反应1小时，降温至55℃加入5克醋酸，再降至30℃，红薯淀粉、氢氧化钠、3-氯-2-羟丙基三甲基氯化铵和醋酸的质量比为100∶7∶49∶5，In the first step, 200 grams of water, 100 grams of sweet potato starch and 0.6 grams of fungal α-amylase were added to the first reactor and reacted for 2.0 hours at 55°C to obtain degraded sweet potato starch, water, sweet potato starch and fungal α-amylase The mass ratio is 200: 100: 0.6, then 7 grams of sodium hydroxide are added to the first reactor, and the temperature is raised to 70°C to add 49 grams of 3-chloro-2-hydroxypropyltrimethylammonium chloride, and then the temperature is raised to React at 95°C for 1 hour, cool down to 55°C and add 5 grams of acetic acid, then lower to 30°C, the mass ratio of sweet potato starch, sodium hydroxide, 3-chloro-2-hydroxypropyltrimethylammonium chloride and acetic acid is 100 :7:49:5,
第二步，向第一反应器中加水，调节体系固含量至25%，即得阳离子红薯淀粉乳化剂，In the second step, add water to the first reactor to adjust the solid content of the system to 25%, to obtain a cationic sweet potato starch emulsifier,
第三步，在第二反应器中加入110克阳离子红薯淀粉乳化剂、110克石蜡和120克AKD，其中阳离子红薯淀粉乳化剂、石蜡和AKD的质量比为110∶110∶120，升高温度至75℃，待石蜡和AKD熔融后，搅拌30分钟，在搅拌下加入80℃的热水分散调节至固含量至20%，制得阳离子红薯淀粉AKD亚稳定乳液，将亚稳定乳液经30MPa均质后，冷却至30℃，得到固含量为20%的稳定的阳离子红薯淀粉AKD中/碱性施胶剂，所述的石蜡为半精炼石蜡和精炼石蜡混合物，两者的质量比为2∶3。The 3rd step, in the second reactor, add 110 gram cationic sweet potato starch emulsifiers, 110 gram paraffin and 120 gram AKD, wherein the mass ratio of cationic sweet potato starch emulsifiers, paraffin and AKD is 110: 110: 120, raising temperature to 75°C, after the paraffin and AKD are melted, stir for 30 minutes, add hot water at 80°C under stirring to disperse and adjust the solid content to 20%, and obtain a cationic sweet potato starch AKD metastable emulsion, and put the metastable emulsion through 30MPa homogenization After qualitative, be cooled to 30 ℃, obtain the stable cationic sweet potato starch AKD medium/alkaline sizing agent that solid content is 20%, described paraffin is semi-refined paraffin and refined paraffin mixture, and the mass ratio of the two is 2: 3.
将此阳离子红薯淀粉AKD中/碱性施胶剂用于以100%国内废纸抄造的110克/米2瓦楞原纸中，淀粉用量70千克/吨纸，阳离子红薯淀粉AKD中/碱性施胶剂3.0千克/吨纸，表面施胶剂后瓦楞原纸的Cobb值为35克/米2，环压指数为8.5牛·米2/克,裂断长为5.0千米，达到A级高强瓦楞原纸质量标准，用阳离子红薯淀粉AKD中/碱性施胶剂施胶后，每吨瓦楞原纸的施胶成本降低了4元。Use this cationic sweet potato starch AKD medium/alkaline sizing agent for 110 g/m2 corrugated base paper made of 100% domestic waste paper, the amount of starch is 70 kg/ton paper, cationic sweet potato starch AKD medium/alkaline sizing 3.0 kg/ton of paper, the Cobb value of the corrugated base paper after surface sizing is 35 g/m2 , the ring pressure index is 8.5 N·m2 /g, and the breaking length is 5.0 km, reaching A-grade high-strength corrugated base paper Quality standard, after sizing with cationic sweet potato starch AKD medium/alkaline sizing agent, the sizing cost per ton of corrugated base paper is reduced by 4 yuan.
综上所述，本发明采用红薯淀粉降解后进行阳离子化，将其作为乳化剂应用于AKD和石蜡的乳化，制备的AKD中/碱性施胶剂乳液粘度小，稳定性好，制备的乳液颗粒带阳电荷，有助于留着并且与带负电荷的纸张纤维能够紧密结合，不但提高乳液稳定性能和施胶性能，并且降低了施胶成本。In summary, the present invention adopts sweet potato starch to be degraded and cationized, and it is used as an emulsifier to emulsify AKD and paraffin wax. The prepared AKD medium/alkaline sizing agent emulsion has low viscosity and good stability, and the prepared emulsion The particles are positively charged, which is helpful for retention and can be closely combined with negatively charged paper fibers, which not only improves the stability of the emulsion and sizing performance, but also reduces the cost of sizing.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101362161ACN102635029A (en) | 2012-05-04 | 2012-05-04 | Preparation method of cation sweet potato starch AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101362161ACN102635029A (en) | 2012-05-04 | 2012-05-04 | Preparation method of cation sweet potato starch AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent |
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| CN102635029Atrue CN102635029A (en) | 2012-08-15 |
| Application Number | Title | Priority Date | Filing Date |
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| CN2012101362161APendingCN102635029A (en) | 2012-05-04 | 2012-05-04 | Preparation method of cation sweet potato starch AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent |
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| CN104452450A (en)* | 2014-11-06 | 2015-03-25 | 江苏理文造纸有限公司 | High-gluing rapid curing type AKD (alkyl ketene dimer) emulsion and papermaking process using same |
| CN114960281A (en)* | 2022-05-26 | 2022-08-30 | 安徽海逸生物科技有限公司 | Method for processing special high-stability internal sizing agent for corrugated case board paper |
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| WO2007086803A1 (en)* | 2006-01-25 | 2007-08-02 | Stora Enso Ab | Sizing composition, method for the production of sized paper or paperboard and sized paper or paperboard |
| CN101168940A (en)* | 2007-12-04 | 2008-04-30 | 天津科技大学 | Preparation method of paraffin wax/AKD compound neutral paper-making sizing agent |
| CN102337707A (en)* | 2011-09-29 | 2012-02-01 | 浙江展航生物科技有限公司 | Preparation method of modified AKD (Alkyl Ketene Dimer) neutral sizing agent |
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| WO2007086803A1 (en)* | 2006-01-25 | 2007-08-02 | Stora Enso Ab | Sizing composition, method for the production of sized paper or paperboard and sized paper or paperboard |
| CN101168940A (en)* | 2007-12-04 | 2008-04-30 | 天津科技大学 | Preparation method of paraffin wax/AKD compound neutral paper-making sizing agent |
| CN102337707A (en)* | 2011-09-29 | 2012-02-01 | 浙江展航生物科技有限公司 | Preparation method of modified AKD (Alkyl Ketene Dimer) neutral sizing agent |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104452450A (en)* | 2014-11-06 | 2015-03-25 | 江苏理文造纸有限公司 | High-gluing rapid curing type AKD (alkyl ketene dimer) emulsion and papermaking process using same |
| CN104452450B (en)* | 2014-11-06 | 2017-04-05 | 江苏理文造纸有限公司 | High applying glue rapid maturing type AKD emulsions and the paper technology using the emulsion |
| CN114960281A (en)* | 2022-05-26 | 2022-08-30 | 安徽海逸生物科技有限公司 | Method for processing special high-stability internal sizing agent for corrugated case board paper |
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| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20120815 |