氧化淀粉及其粘合剂的制备和性能研究
摘要
本研究主要是以马铃薯淀粉为原料,硫酸亚铁为催化剂,双氧水为氧化剂,制备氧化淀粉,再在氧化淀粉中加碱糊化,加入交联剂进行交联改性,降温后依次添加稀释剂、增塑剂、消泡剂等助剂,最终得到一种环保的、成本较低的、性能优良的淀粉基瓦楞纸板用粘合剂。论文主要对氧化淀粉的制备和表征、粘合剂的配方和制备工艺以及粘合剂的性能进行了研究,并对淀粉粘合剂的快干改性进行了研究。
首先,对双氧水氧化制备马铃薯氧化淀粉进行研究,利用红外光谱、X-射线粉末衍射和扫描电镜等手段对氧化淀粉进行了表征,通过单因素实验研究了反应温度、双氧水用量、催化剂用量和反应时间等影响因素对氧化淀粉的羧基含量、羰基含量等指标的影响,结果表明:用H202-FeS04氧化还原体系氧化时对淀粉的晶型结构破坏很小,氧化反应主要发生在淀粉的非结晶区,只有少量发生在结晶区;淀粉30g,氧化剂(质量分数为30%的H2O2)的用量为1.6mL、催化剂(无水FeSO4)的用量为0.1g、反应时间为60min、反应温度为35℃,羧基、羰基含量最大。
其次以马铃薯淀粉为原料,热法制得淀粉基无甲醛粘合剂。并探索热法制淀粉基无甲醛粘合剂的最佳原料配比和工艺条件。其中共包括两部分内容。
(1)通过正交实验法初步确定淀粉粘合剂的原料配比和工艺条件,以及确定淀粉粘合剂性能的重要影响因素。
(2)通过单因素实验,对影响淀粉粘合剂的初粘力,粘合强度和稳定性等各性能的主要因素进行了分析和研究,进一步改进淀粉粘合剂的原料配比和工艺条件,从而确定最佳的原料配比和工艺条件。
实验研究表明:取淀粉30g,通过正交试验确定淀粉粘合剂的最佳配比是:氧化剂(质量分数为30%的H2O2)的用量为1.6mL、催化剂(无水FeSO4)的用量为0.1g、水的用量为150g、糊化剂(NaOH)的用量2.7g,氧化时间为60min、交联剂(硼砂)的用量0.3g,糊化时间为30min,通过单因素实验进一步确定各影响因素对粘合剂粘合强度,粘度,初粘力以及稳定性的影响,确定通过正交实验确定的配比为最佳配比,得到粘合剂的粘合强度为8.65 N/cm2,粘度为39.25s,起毛面积为100%,远远超过标准规定粘合剂剥离强度不小于6.0N/cm2 [95]的要求。
最后通过对淀粉粘合剂的进行添加不同质量的钠基膨润土和聚乙烯醇的催干改性的对比研究,我们发现选用聚乙烯醇改性的淀粉粘合剂性能稳定,粘合强度高,干燥速度快,最后选择聚乙烯醇作为催干剂对原有的原料配比进行快干改性,并通过实验得知,随聚乙烯醇添加量的不同,其影响效果大小也不同,综合考虑其对淀粉粘合剂的干燥速度的影响及成本因素,选择有机催干剂聚乙烯醇添加量为淀粉粘合剂总质量的5%作为最佳添加量。
氧化淀粉粘合剂广泛运用于造纸,纺织等领域,而马铃薯淀粉又是绿色可再生资源,对氧化马铃薯淀粉粘合剂的研究有着深刻的意义。
The research first synthesizes oxidized starch which preparation procedure uses potato starch as raw material, ferrous sulfate as catalyst, and chooses hydrogen peroxide as oxidizer. And then, adds base for gelatinization, crosslinking agent for crosslinking modification. After the mixture cooling down, diluting agent, plasticizer, defoaming agents, etc. have been added consecutively. Finally, an environment-friendly, low cost, and premium properties’starch-base adhesive for corrugated fiberboard was produced. In this paper, the study is mainly about the preparation and characterization of oxidized starch; the formula and preparation technology of adhesive, as well as its performance; besides, quick-drying modification of starch adhesive is also part of the study.
Firstly, the research focuses on the preparative of potato starch by hydrogen peroxide, Oxidized starch was characterized by IR,XRD and SEM.The temperature of reaction; the dosage of hydrogen peroxide; the dosage of catalyst; the reaction time are the factors of effect on oxidized starch’s hydroxyl content and carbonyl group index, and these were studied via single-factor experiment. The results show that the xoidation-reduction system of H2O2-FeSO4 is hard to break up the cyrstalline phase of starch,and the oxidation reaction occur major in amorphous region. starch charge 30g, oxidizer (30% H2O2)charge 1.6mL, catalyst (FeSO4)charge 0.1 g, reaction time 60min, reaction temperature 35℃, the degree of oxidation of starch and the content of cabroxyl group as well as cabronyl group were maxlmum.
Using potato starch as raw material, prepare starch- base nonformaldehyde adhesive by thermal method. This research also discovers the optimal raw material configuration and process conditions under thermal method, and it contains two parts.
(1) By orthogonal experiment, the optimal raw material configuration and process conditions of adhesive, as well as the factors of effect on performance of adhesive product were defined.
(2) Via single-factor experiment, the influencing factors of starch adhesive’s initial viscosity, adhesive strength, stability and other characteristic were analyzed and studied. In addition, by doing so, the raw material configuration and process conditions of starch adhesive were improved, and its optimal condition were determined.
Based on the experiment, using 30g starch, the optimal proportioning of starch adhesive which determined by orthogonal experiment, were as follows: oxidizer (30% H2O2) charges 1.6mL, catalyst (FeSO4) charges 0.1g, water charges 150g, gelatinization agent (NaOH) charges 2.7g, oxidized time costs 60min, crosslinking agent (borax) charges 0.3g and gelatinized time costs 30min. Through the single-factor experiment, the effect factors on adhesive strength, viscosity, initial tack and stability of adhesive, were further more ascertained. Subsequently, based on above, the optimal proportioning is determined under the orthogonal experiment, and the obtained adhesive product parameters are: adhesive strength 8.65N/cm2, viscosity 39.25s, and fluffed area 100%. The adhesive far more than the demands of standard provisions of adhesive peel strength ,which is not less than 6.0N/cm2 [95].
Ultimately, I added different quantity of Sodium Bentonite and polyvinyl alcohal as additives to improve properties.The result of experiment shows that the starch adhesive modified with polyvinyl alcohal are stable,and that the Adhesive strength of the starch adhesive modified adhesive is improved.It could bedried quickly. Final we choose polyvinyl alcohal as drier for quick-drying modified in the original ratio of raw materials. Based on the experiment, different dosages of addictive have different effects. And being comprehensively consideration, its effects on drying speed, as well as its cost, the optimal dosage of addictive is 5% of the starch adhesive’s total mass.
Oxidized starch is broad applied in many fields such as papermaking and textile. What’s more, potato starch is a kind of green and renewable resource, thus, the study on potato starch adhesive has significant importance.
首先,对双氧水氧化制备马铃薯氧化淀粉进行研究,利用红外光谱、X-射线粉末衍射和扫描电镜等手段对氧化淀粉进行了表征,通过单因素实验研究了反应温度、双氧水用量、催化剂用量和反应时间等影响因素对氧化淀粉的羧基含量、羰基含量等指标的影响,结果表明:用H202-FeS04氧化还原体系氧化时对淀粉的晶型结构破坏很小,氧化反应主要发生在淀粉的非结晶区,只有少量发生在结晶区;淀粉30g,氧化剂(质量分数为30%的H2O2)的用量为1.6mL、催化剂(无水FeSO4)的用量为0.1g、反应时间为60min、反应温度为35℃,羧基、羰基含量最大。
其次以马铃薯淀粉为原料,热法制得淀粉基无甲醛粘合剂。并探索热法制淀粉基无甲醛粘合剂的最佳原料配比和工艺条件。其中共包括两部分内容。
(1)通过正交实验法初步确定淀粉粘合剂的原料配比和工艺条件,以及确定淀粉粘合剂性能的重要影响因素。
(2)通过单因素实验,对影响淀粉粘合剂的初粘力,粘合强度和稳定性等各性能的主要因素进行了分析和研究,进一步改进淀粉粘合剂的原料配比和工艺条件,从而确定最佳的原料配比和工艺条件。
实验研究表明:取淀粉30g,通过正交试验确定淀粉粘合剂的最佳配比是:氧化剂(质量分数为30%的H2O2)的用量为1.6mL、催化剂(无水FeSO4)的用量为0.1g、水的用量为150g、糊化剂(NaOH)的用量2.7g,氧化时间为60min、交联剂(硼砂)的用量0.3g,糊化时间为30min,通过单因素实验进一步确定各影响因素对粘合剂粘合强度,粘度,初粘力以及稳定性的影响,确定通过正交实验确定的配比为最佳配比,得到粘合剂的粘合强度为8.65 N/cm2,粘度为39.25s,起毛面积为100%,远远超过标准规定粘合剂剥离强度不小于6.0N/cm2 [95]的要求。
最后通过对淀粉粘合剂的进行添加不同质量的钠基膨润土和聚乙烯醇的催干改性的对比研究,我们发现选用聚乙烯醇改性的淀粉粘合剂性能稳定,粘合强度高,干燥速度快,最后选择聚乙烯醇作为催干剂对原有的原料配比进行快干改性,并通过实验得知,随聚乙烯醇添加量的不同,其影响效果大小也不同,综合考虑其对淀粉粘合剂的干燥速度的影响及成本因素,选择有机催干剂聚乙烯醇添加量为淀粉粘合剂总质量的5%作为最佳添加量。
氧化淀粉粘合剂广泛运用于造纸,纺织等领域,而马铃薯淀粉又是绿色可再生资源,对氧化马铃薯淀粉粘合剂的研究有着深刻的意义。
The research first synthesizes oxidized starch which preparation procedure uses potato starch as raw material, ferrous sulfate as catalyst, and chooses hydrogen peroxide as oxidizer. And then, adds base for gelatinization, crosslinking agent for crosslinking modification. After the mixture cooling down, diluting agent, plasticizer, defoaming agents, etc. have been added consecutively. Finally, an environment-friendly, low cost, and premium properties’starch-base adhesive for corrugated fiberboard was produced. In this paper, the study is mainly about the preparation and characterization of oxidized starch; the formula and preparation technology of adhesive, as well as its performance; besides, quick-drying modification of starch adhesive is also part of the study.
Firstly, the research focuses on the preparative of potato starch by hydrogen peroxide, Oxidized starch was characterized by IR,XRD and SEM.The temperature of reaction; the dosage of hydrogen peroxide; the dosage of catalyst; the reaction time are the factors of effect on oxidized starch’s hydroxyl content and carbonyl group index, and these were studied via single-factor experiment. The results show that the xoidation-reduction system of H2O2-FeSO4 is hard to break up the cyrstalline phase of starch,and the oxidation reaction occur major in amorphous region. starch charge 30g, oxidizer (30% H2O2)charge 1.6mL, catalyst (FeSO4)charge 0.1 g, reaction time 60min, reaction temperature 35℃, the degree of oxidation of starch and the content of cabroxyl group as well as cabronyl group were maxlmum.
Using potato starch as raw material, prepare starch- base nonformaldehyde adhesive by thermal method. This research also discovers the optimal raw material configuration and process conditions under thermal method, and it contains two parts.
(1) By orthogonal experiment, the optimal raw material configuration and process conditions of adhesive, as well as the factors of effect on performance of adhesive product were defined.
(2) Via single-factor experiment, the influencing factors of starch adhesive’s initial viscosity, adhesive strength, stability and other characteristic were analyzed and studied. In addition, by doing so, the raw material configuration and process conditions of starch adhesive were improved, and its optimal condition were determined.
Based on the experiment, using 30g starch, the optimal proportioning of starch adhesive which determined by orthogonal experiment, were as follows: oxidizer (30% H2O2) charges 1.6mL, catalyst (FeSO4) charges 0.1g, water charges 150g, gelatinization agent (NaOH) charges 2.7g, oxidized time costs 60min, crosslinking agent (borax) charges 0.3g and gelatinized time costs 30min. Through the single-factor experiment, the effect factors on adhesive strength, viscosity, initial tack and stability of adhesive, were further more ascertained. Subsequently, based on above, the optimal proportioning is determined under the orthogonal experiment, and the obtained adhesive product parameters are: adhesive strength 8.65N/cm2, viscosity 39.25s, and fluffed area 100%. The adhesive far more than the demands of standard provisions of adhesive peel strength ,which is not less than 6.0N/cm2 [95].
Ultimately, I added different quantity of Sodium Bentonite and polyvinyl alcohal as additives to improve properties.The result of experiment shows that the starch adhesive modified with polyvinyl alcohal are stable,and that the Adhesive strength of the starch adhesive modified adhesive is improved.It could bedried quickly. Final we choose polyvinyl alcohal as drier for quick-drying modified in the original ratio of raw materials. Based on the experiment, different dosages of addictive have different effects. And being comprehensively consideration, its effects on drying speed, as well as its cost, the optimal dosage of addictive is 5% of the starch adhesive’s total mass.
Oxidized starch is broad applied in many fields such as papermaking and textile. What’s more, potato starch is a kind of green and renewable resource, thus, the study on potato starch adhesive has significant importance.
引文
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