CN113512172B - 一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇 - Google Patents
一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇 Download PDFInfo
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- CN113512172B CN113512172B CN202110614323.XA CN202110614323A CN113512172B CN 113512172 B CN113512172 B CN 113512172B CN 202110614323 A CN202110614323 A CN 202110614323A CN 113512172 B CN113512172 B CN 113512172B
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- polyester polyol
- fatty acid
- sebacic acid
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 title claims abstract description 166
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- 239000006227 byproduct Substances 0.000 title claims abstract description 84
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 42
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 15
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- 239000012974 tin catalyst Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 38
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- 238000000034 method Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- Fertilizers (AREA)
Abstract
本发明公开了一种以葵二酸副产脂肪酸合成的聚酯多元醇聚氨酯控释肥膜材料,涉及控释肥包膜材料技术领域。本发明是通过葵二酸副产脂肪酸与苯二甲酸(酐)、二甘醇或二甘醇和甘油、己二酸等合成高性能生物基聚酯多元醇,再与聚合MDI在肥料表面进行交联成膜,葵二酸副产脂肪酸为蓖麻油生产葵二酸所得副产品物精制而成,价格低廉,使用葵二酸副产脂肪酸合成的聚酯多元醇制得的控释肥,不仅产品性能优良,而且经济,具有非常好的性价比,施入土壤后降解好,是高性能、低成本和环保的完美结合,同时也是对葵二酸副产品进行综合利用的有效举措。
Description
技术领域
本发明涉及控释肥包膜材料技术领域,具体涉及一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇。
背景技术
癸二酸是制造尼龙纤维的主要原料,我国的癸二酸产量约占世界的百分之九十,目前国内的制备方法是以蓖麻油为原料。蓖麻油经过水解、裂解、酸化等步骤制得,在生产过程中产生出大量副产物,这些副产物主要含一些脂肪酸及其钠皂,同时含水、酚和有机聚合物成分。脂肪酸是癸二酸生产过程中主要的副产品(简称癸脂),占癸二酸产量的60%,这种副产品脂肪酸由于经过高温裂化,它的组成与构成原油脂的脂肪酸组分及性质发生了根本性变化,且其中增加了对环境和人体十分有害的酚类物质。由于组成复杂,分离困难,通常废弃掉,一方面造成环境污染,另一方面副产物中含有的有价值的脂肪酸没能得到充分利用将是极大的浪费。脂肪酸的附加值很低,价格低廉,且无销路,大量积压,对癸二酸生产造成了很大的负担。
癸二酸副产脂肪酸目前主要用途:可用于合成润滑脂,润滑剂和表面活性剂,制备生物柴油,制皂的原料,甚至被丢弃,工业价值不高。而以癸二酸副产脂肪酸合成聚酯多元醇的聚氨酯控释膜材料,几乎没有报道。
专利号为201210137099.0的中国发明专利公开了一种利用地沟油制备聚酯多元醇的方法,包括以下步骤:将地沟油、催化剂和起始剂混合反应1~5小时,反应过程中通氮气或者惰性气体保护,并加温至100~300°C;把上述步骤反应得到的产物和苯酐混合反应5~10小时,反应过程中通氮气或者惰性气体保护,并加温至100~300°C;把上述步骤的反应产物和碳酸钠混合反应1~3小时,反应过程中抽真空脱水,并加温至100~150°C,真空度小于0.08MPa。本发明虽然可以利用地沟油制备聚酯多元醇,但是由于地沟油的成分复杂、不稳定,而且生产成本高,工艺复杂,因此该方法并不能被广泛使用。
专利号为201310655152.0的中国发明专利公开了一种利用回收醇和地沟油制备地沟油改性聚酯多元醇的方法。本发明将低分子多元醇原料与地沟油和催化剂投入聚酯反应釜中;升温至140~150℃,反应1~1.5h;通N2,继续升温至180~190℃,反应1.5~2h;继续升温至220~230℃,保温4~5h;停止加热,降温至120℃,关闭氮气,抽真空,反应1.5~2h,待产物水分≤0.07时停止反应;最后,冷却至75℃以下出料。该方法工艺复杂,且产物性能不稳定,不适宜推广。
专利号为201610370195.8的中国发明专利公开了一种蓖麻油聚酯多元醇的制备及其在控释肥中的应用。以蓖麻油为原料,小分子醇为改性剂,催化剂作用下通过酯交换反应制备高羟值蓖麻油多元醇,然后以多元酸或者酐为改性剂,催化缩合反应,制得羟值为200-350mgKOH/g的蓖麻油聚酯多元醇。以蓖麻油聚酯多元醇为白料,异氰酸酯为黑料,通过原位反应制备包膜控释肥。该方法对蓖麻油进行改性制备聚酯多元醇,进一步制得包膜控释肥,蓖麻油改性过程不可控,而且蓖麻油价格相对较高,增加了生产成本。
发明内容
为解决上述问题及充分开发癸二酸副产脂肪酸的新用途,本发明提供一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇,本发明合成的产品结构性能稳定,成本低,质量优,而且可降解,对环境友好。
具体的,本发明是通过以下的技术方案来实现的:
一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇,该聚氨酯控释肥膜材料中的组分聚酯多元醇是使用癸二酸副产脂肪酸和其他原料反应而成,癸二酸副产脂肪酸是由蓖麻油生产癸二酸所产生的副产精制而成;所述癸二酸副产脂肪酸主要成分为C18H34O3、C18不饱和脂肪酸C18H34O2、C16不饱和脂肪酸C16H30O2三种脂肪酸;
其中,C18H34O3的结构式为:
C18H34O2的结构式为:
C16H30O2的结构式为:
进一步地,当上述聚酯多元醇是由癸二酸副产脂肪酸、苯二甲酸和醇反应时,其配方为癸二酸副产脂肪酸、苯二甲酸、二甘醇、甘油、己二酸反应合成的聚酯多元醇,聚酯多元醇的羟值为170-350 mgKOH/g。
优选地,苯二甲酸包括对苯二甲酸、邻苯二甲酸(酐)以及间苯二甲酸;
更进一步地,上述分子结构式中n值均等于15或17。
进一步地,聚酯多元醇的合成方法包括以下步骤:
(1)首先将癸二酸副产脂肪酸和甘油置于反应器中,然后加热到160~240℃,进行酯化反应,并且在160~240℃保温1~6小时,待酸值降至10mgKOH/g以下后降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
(2)将二甘醇、甘油、苯二甲酸(酐)、步骤(1)中得到的癸二酸副产脂肪酸甘油酯加入反应容器中,然后再加入催化剂加热回流反应,220~260℃保温并检测酸值,当酸值降到5mgKOH/g以下后,降温到180~220℃,开始真空精馏,真空度控制在-0.065~-0.095,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量份数低于0.1%后降温出料,即得聚酯多元醇。
更进一步地,上述聚酯多元醇的合成方法步骤(1)中,癸二酸副产脂肪酸和甘油的摩尔比为1:(1~1.5)。
更进一步地,上述聚酯多元醇的合成方法步骤(2)中,各反应物重量比为:二甘醇、甘油:20~50%;苯二甲酸(酐):30~40%;癸二酸副产脂肪酸甘油酯:20~50%。
优选地,上述聚酯多元醇的合成方法中催化剂为酯化催化剂;酯化催化剂包括有机钛酸酯类催化剂、有机锡类催化剂、氧化钙、醋酸锌中的任一种;有机钛酸酯类催化剂为钛酸异丙酯、钛酸丁酯中的任一种。
与现有技术相比,本发明的至少存在以下的有益效果:
1、本发明的聚酯多元醇主要原料是癸二酸副产脂肪酸,由于副产脂肪酸应用有限,甚至被丢弃,造成了极大的浪费和环境污染,本发明不仅可以开发脂肪酸的新用途,还能缓解癸二酸生产的压力,起到副产再利用,变废为宝的效果。
2、本发明利用上述新型聚酯多元醇制得的聚氨酯包膜控释肥料,其表面的聚氨酯膜是一种新型生物基可降解包膜材料,检测报告结果显示:控释肥膜材生物分解率可达到31.2%。包衣率为2.0%-3.5%,释放期可以达到60-150天,满足各种作物生长所需养分,可以对植物生长起到很好的控释作用,且包膜材料可降解,对环境无污染,对土壤没有危害,具有广泛推广的应用价值。
3、本发明研究了一种新材料,即以癸二酸副产脂肪酸为原料,合成聚酯多元醇以及利用该聚酯多元醇制备得到一种新型的聚氨酯控释肥包膜材料,其中,癸二酸副产脂肪酸为蓖麻油生产癸二酸所得副产品物精制而成,价格低廉,来源广泛,价格在4000-5000元/吨,远远低于蓖麻油的11000-15000元/吨的价格,也低于常规植物油(大豆油、棕榈油、亚麻油等),制得的聚酯多元醇价格为6000-7000元/吨,因此生产成本很低;而使用上述癸二酸副产脂肪酸合成的聚酯多元醇制得的聚氨酯包膜控释肥料,不仅产品性能优良,而且经济,具有非常好的性价比及价格优势,可大大提高市场同类产品的竞争力,且该聚氨酯包膜控释肥料施入土壤后降解好,是高性能、低成本及环保的完美结合,同时还能够将癸二酸副产品进行综合有效的利用,一举多得,具有意想不到的技术效果。
4、本发明制备得到的聚氨酯控释肥包膜材料,具有成分稳定、结构稳定、性能稳定的优势,产品质量稳定,农户可以放心使用。
具体实施方式
下面结合实施例对本发明的具体实施方式作进一步描述,以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
实施例1
一、一种癸二酸副产聚酯多元醇的生产方法,该方法包括如下步骤:
1)首先将1mol癸二酸副产脂肪酸和1mol甘油置于反应器中,然后加热到160℃,进行酯化反应,并且在160℃保温3小时,待酸值降至1.50mgKOH/g时降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
2)将330g二甘醇、10g甘油、100g邻苯二甲酸酐、300g对苯二甲酸、260g步骤1)中得到的癸二酸副产脂肪酸甘油酯,加入反应容器中,然后再加入钛酸异丙酯催化剂加热回流反应,220℃保温并检测酸值,当酸值降到1.50mgKOH/g时,降温到180℃,开始真空精馏,真空度控制在-0.065~-0.095mPa,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量分数达0.08%时降温出料,即得到聚酯多元醇。
二、按照GB/T12008.3-2009标准,采用邻苯二甲酸酐法进行测定,所得聚酯多元醇的羟值为180.5mgKOH/g,粘度为15100CPS/25℃。
实施例2
一、一种利用实施例1合成的聚酯多元醇制备聚氨酯包膜控释肥料的方法,包括以下步骤:
称取粒径2.00mm-4.75mm的颗粒尿素1公斤加入到糖衣机进行加热,加热温度为60℃;将2.8g聚合MDI和4.2g聚酯多元醇混合搅拌后,加入到颗粒尿素表面,聚氨酯膜在颗粒尿素表面开始交联反应,粘度提高,待包衣材料在尿素表面逐渐固化3-5分钟散开后,形成致密坚韧的聚氨酯膜,包衣率为0.7%。重复3次,第二次和第三次分别加入2.8g聚合MDI和4.2g聚酯多元醇,直至包衣率为2.1%。最后加入肥料总质量的0.2%的石蜡以防止肥料颗粒之间发生粘连,冷却至20℃后,即制得以癸二酸副产脂肪酸合成的聚酯多元醇聚氨酯包膜尿素。
二、包膜控释肥料的控释性能测试
在25℃的条件下,采用静水浸提法测试包膜控释肥料的养分释放期,以累积养分释放率达到80%时所需天数来表示。
本实施例2所制备的包膜控释肥料的养分释放期为60天。
为了说明本实施例包膜材料的生物降解性能,将实施例2中包膜材料准确称量后埋入58℃±2℃土壤中,6个月后取样,清洗掉表面的泥土后真空干燥24h,称重,计算出试样重量损失率达31.2%。
实施例3
一、一种癸二酸副产聚酯多元醇的生产方法,该方法包括如下步骤:
1)首先将1mol癸二酸副产脂肪酸和1mol甘油置于反应器中,然后加热到180℃,进行酯化反应,并且在180℃保温3小时,待酸值降至1.50mgKOH/g时降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
2)将350g二甘醇、10g甘油、200g间苯二甲酸、200g对苯二甲酸、300g步骤1)中得到的癸二酸副产脂肪酸甘油酯,加入反应容器中,然后再加入有机锡类催化剂加热回流反应,230℃保温并检测酸值,当酸值降到1.63mgKOH/g以下后,降温到190℃,开始真空精馏,真空度控制在-0.065~-0.095mPa,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量分数达0.06%时降温出料,即得到聚酯多元醇。
二、按照GB/T12008.3-2009标准,采用邻苯二甲酸酐法进行测定,所得聚酯多元醇的羟值为207.3mgKOH/g,粘度为12300CPS/25℃。
实施例4
一、一种利用实施例3合成的聚酯多元醇制备聚氨酯包膜控释肥料的方法,包括以下步骤:
称取粒径2.00mm-4.75mm的颗粒尿素1公斤加入到糖衣机进行加热,加热温度为62℃;将2.8g聚合MDI和4.2g聚酯多元醇混合搅拌后,加入到颗粒尿素表面,聚氨酯膜在颗粒尿素表面开始交联反应,粘度提高,待包衣材料在尿素表面逐渐固化3-5分钟散开后,形成致密坚韧的聚氨酯膜,包衣率为0.7%。重复3次,第二次和第三次分别加入2.8g聚合MDI和4.2g聚酯多元醇,直至包衣率为2.1%。最后加入肥料总质量的0.2%的石蜡以防止肥料颗粒之间发生粘连,冷却至20℃,即制得以癸二酸副产脂肪酸合成的聚酯多元醇聚氨酯包膜尿素。
二、包膜控释肥料的控释性能测试
具体测试方法同实施例2。
本实施例4所制备的包膜控释肥料的养分释放期为60天。
实施例5
一、一种癸二酸副产聚酯多元醇的生产方法,该方法包括如下步骤:
1)首先将1mol癸二酸副产脂肪酸和1.2mol甘油置于反应器中,然后加热到200℃,进行酯化反应,并且在200℃保温4小时,待酸值降至1.17mgKOH/g时降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
2)将260g二甘醇、20g甘油、250g邻苯二甲酸、50g间苯二甲酸、430g步骤1)中得到的癸二酸副产脂肪酸甘油酯,加入反应容器中,然后再加入钛酸丁酯催化剂加热回流反应,240℃保温并检测酸值,当酸值降到1.17mgKOH/g以下后,降温到200℃,开始真空精馏,真空度控制在-0.065~-0.095mPa,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量分数达0.07%时降温出料,即得到聚酯多元醇。
二、按照GB/T12008.3-2009标准,采用邻苯二甲酸酐法进行测定,所得聚酯多元醇的羟值为266.9mgKOH/g,粘度为2860CPS/25℃。
实施例6
一、一种利用实施例5合成的聚酯多元醇制备聚氨酯包膜控释肥料的方法,包括以下步骤:
称取粒径2.00mm-4.75mm的颗粒尿素1公斤加入到糖衣机进行加热,加热温度为62℃;将3.6g聚合MDI和5.4g聚酯多元醇混合搅拌后,加入到颗粒尿素表面,聚氨酯膜在颗粒尿素表面开始交联反应,粘度提高,待包衣材料在尿素表面逐渐固化3-5分钟散开后,形成致密坚韧的聚氨酯膜,包衣率为0.9%。第二次和第三次分别加入3.2g聚合MDI和4.8g聚酯多元醇,包衣率均为0.8%,最终包衣率为2.5%。最后加入肥料总质量的0.2%的石蜡以防止肥料颗粒之间发生粘连,冷却至20℃,即制得以癸二酸副产脂肪酸合成的聚酯多元醇聚氨酯包膜尿素。
二、包膜控释肥料的控释性能测试
具体测试方法同实施例2。
本实施例6所制备的包膜控释肥料的养分释放期为90天。
实施例7
一、一种癸二酸副产聚酯多元醇的生产方法,该方法包括如下步骤:
1)首先将1mol癸二酸副产脂肪酸和1.2mol甘油置于反应器中,然后加热到220℃,进行酯化反应,并且在220℃保温4小时,待酸值降至0.98mgKOH/g时降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
2)将300g二甘醇、50g甘油、200g邻苯二甲酸、100g对苯二甲酸、430g步骤1)中得到的癸二酸副产脂肪酸甘油酯,加入反应容器中,然后再加入氧化钙催化剂加热回流反应,250℃保温并检测酸值,当酸值降到0.98mgKOH/g以下后,降温到210℃,开始真空精馏,真空度控制在-0.065~-0.095mPa,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量分数达0.06%时降温出料,即得到聚酯多元醇。
二、按照GB/T12008.3-2009标准,采用邻苯二甲酸酐法进行测定,所得聚酯多元醇的羟值为347.6mgKOH/g,粘度为1760CPS/25℃。
实施例8
一、一种利用实施例7合成的聚酯多元醇制备聚氨酯包膜控释肥料的方法,包括以下步骤:
称取粒径2.00mm-4.75mm的颗粒尿素1公斤加入到糖衣机进行加热,加热温度为65℃;将3.2g聚合MDI和4.8g聚酯多元醇混合搅拌后,加入到颗粒尿素表面,聚氨酯膜在颗粒尿素表面开始交联反应,粘度提高,待包衣材料在尿素表面逐渐固化3-5分钟散开后,形成致密坚韧的聚氨酯膜,包衣率为0.8%。然后第二次加入3.2g聚合MDI和4.8g聚酯多元醇,包衣率为0.8%。第三次加入3.6g聚合MDI和5.4g聚酯多元醇,包衣率为0.9%,最终包衣率达到2.5%。最后加入肥料总质量的0.2%的石蜡以防止肥料颗粒之间发生粘连,冷却至20℃,即制得以癸二酸副产脂肪酸合成的聚酯多元醇聚氨酯包膜尿素。
二、包膜控释肥料的控释性能测试
具体测试方法同实施例2。
本实施例8所制备的包膜控释肥料的养分释放期为90天。
实施例9
一、一种癸二酸副产聚酯多元醇的生产方法,该方法包括如下步骤:
1)首先将1mol癸二酸副产脂肪酸和1.5mol甘油置于反应器中,然后加热到240℃,进行酯化反应,并且在240℃保温5小时,待酸值降至1.24mgKOH/g时降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
2)将200g二甘醇、20g甘油、200g邻苯二甲酸、100g对苯二甲酸、500g步骤1)中得到的癸二酸副产脂肪酸甘油酯,加入反应容器中,然后再加入醋酸锌催化剂加热回流反应,260℃保温并检测酸值,当酸值降到1.24mgKOH/g以下后,降温到220℃,开始真空精馏,真空度控制在-0.065~-0.095mPa,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量分数达0.05%时降温出料,即得到聚酯多元醇。
二、按照GB/T12008.3-2009标准,采用邻苯二甲酸酐法进行测定,所得聚酯多元醇的羟值为277.5mgKOH/g,粘度为3530CPS/25℃。
实施例10
一、一种利用实施例9合成的聚酯多元醇制备聚氨酯包膜控释肥料的方法,包括以下步骤:
称取粒径2.00mm-4.75mm的颗粒尿素1公斤加入到糖衣机进行加热,加热温度为65℃;将2.8g聚合MDI和4.2g聚酯多元醇混合搅拌后,加入到颗粒尿素表面,聚氨酯膜在颗粒尿素表面开始交联反应,粘度提高,待包衣材料在尿素表面逐渐固化3-5分钟散开后,形成致密坚韧的聚氨酯膜,包衣率为1.0%。重复3次,第二次和第三次分别加入4g聚合MDI和6g聚酯多元醇,直至包衣率为3.0%。最后加入肥料总质量的0.2%的石蜡以防止肥料颗粒之间发生粘连,冷却至20℃,即制得以癸二酸副产脂肪酸合成的聚酯多元醇聚氨酯包膜尿素。
二、包膜控释肥料的控释性能测试
具体测试方法同实施例2。
本实施例10所制备的包膜控释肥料的养分释放期为120天。
实施例11
一、一种癸二酸副产聚酯多元醇的生产方法,该方法包括如下步骤:
1)首先将1mol癸二酸副产脂肪酸和1.5mol甘油置于反应器中,然后加热到200℃,进行酯化反应,并且在200℃保温5小时,待酸值降至1.04mgKOH/g时降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
2)将200g二甘醇、30g甘油、300g邻苯二甲酸、56g间苯二甲酸、350g步骤1)中得到的癸二酸副产脂肪酸甘油酯,加入反应容器中,然后再加入有机锡类催化剂加热回流反应,240℃保温并检测酸值,当酸值降到1.04mgKOH/g以下后,降温到200℃,开始真空精馏,真空度控制在-0.065~-0.095mPa,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量分数达0.07%时降温出料,即得到聚酯多元醇。
二、按照GB/T12008.3-2009标准,采用邻苯二甲酸酐法进行测定,所得聚酯多元醇的羟值为181.4mgKOH/g,粘度为23500CPS/25℃。
实施例12
一、一种利用实施例11合成的聚酯多元醇制备聚氨酯包膜控释肥料的方法,包括以下步骤:
称取粒径2.00mm-4.75mm的颗粒尿素1公斤加入到糖衣机进行加热,加热温度为68℃;将4.4g聚合MDI和6.6g聚酯多元醇混合搅拌后,加入到颗粒尿素表面,聚氨酯膜在颗粒尿素表面交联反应,粘度提高,待包衣材料在尿素表面逐渐固化3-5分钟散开后,形成致密坚韧的聚氨酯膜,包衣率为1.1%。第二次和第三次分别加入4.8g聚合MDI和7.2g聚酯多元醇,直至包衣率为3.5%。最后加入肥料总质量的0.2%的石蜡以防止肥料颗粒之间发生粘连,冷却至20℃,即制得以癸二酸副产脂肪酸合成的聚酯多元醇聚氨酯包膜尿素。
二、包膜控释肥料的控释性能测试
具体测试方法同实施例2。
本实施例12所制备的包膜控释肥料的养分释放期为150天。
应用实施例
一、样品:实施例2、实施例4、实施例6、实施例8、实施例10、实施例12制备的包膜控释肥料;
二、将实施例2、实施例4、实施例6、实施例8、实施例10、实施例12制备的包膜缓控释肥料产品在25℃的条件下,采用静水浸提法测试包膜缓控释肥料的养分释放期,选取不同的天数取样测定静水中氮素累积释放率,取样测定时间于第24h、7d、28d、56d、60d、90d、120d、150d进行,最后记录以上各实施例的包膜尿素静水浸提氮素累积释放率,具体见下表1所示。
表1:不同实验例中包膜尿素静水浸提氮素累积释放率测定数据
实验组 | 24h氮素初始释放率 | 7d氮素累计释放率 | 28d氮素累计释放率 | 56d氮素累计释放率 | 60d氮素累计释放率 | 90d氮素累计释放率 | 120d氮素累计释放率 | 150d氮素累计释放率 |
实施例2 | 0.19 | 4.13 | 54.61 | 77.90 | 79.09 | |||
实施例4 | 0.22 | 4.22 | 51.12 | 73.45 | 77.62 | |||
实施例6 | 0.15 | 2.34 | 12.07 | 39.16 | 46.01 | 78.43 | ||
实施例8 | 0.18 | 3.37 | 10.19 | 41.48 | 49.15 | 82.87 | ||
实施例10 | 0.03 | 2.41 | 5.26 | 23.91 | 33.69 | 61.25 | 80.96 | |
实施例12 | 0.01 | 1.25 | 4.35 | 15.23 | 21.45 | 40.76 | 62.15 | 81.63 |
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇,其特征在于,所述聚酯多元醇的羟值为170-350 mgKOH/g。
7.根据权利要求2所述的一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇,其特征在于,所述聚酯多元醇的合成方法包括以下步骤:
(1)首先将癸二酸副产脂肪酸和甘油置于反应器中,然后加热到160~240℃,进行酯化反应,并且在160~240℃保温1~6小时,待酸值降至10mgKOH/g以下后降温,得到黄色透明粘稠液体,即为癸二酸副产脂肪酸甘油酯,留后续反应使用;
(2)将二甘醇、甘油、邻苯二甲酸或邻苯二甲酸酐、步骤(1)中得到的癸二酸副产脂肪酸甘油酯加入反应容器中,然后再加入催化剂加热回流反应,220~260℃保温并检测酸值,当酸值降到5mgKOH/g以下后,降温到180~220℃,开始真空精馏,真空度控制在-0.065~-0.095,直至精馏后的产物的酸值降到1.0mgKOH/g以下,水份质量份数低于0.1%后降温出料,即得所述聚酯多元醇。
8.根据权利要求7所述的一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇,其特征在于,步骤(1)中,所述癸二酸副产脂肪酸和甘油的摩尔比为1:(1~1.5)。
9.根据权利要求7所述的一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇,其特征在于,步骤(2)中,各反应物重量比为:二甘醇、甘油:20~50%;邻苯二甲酸或邻苯二甲酸酐:30~40%;癸二酸副产脂肪酸甘油酯:20~50%。
10.根据权利要求7所述的一种聚氨酯控释肥包膜用的癸二酸副产脂肪酸聚酯多元醇,其特征在于,所述催化剂为酯化催化剂;所述酯化催化剂包括有机钛酸酯类催化剂、有机锡类催化剂、氧化钙、醋酸锌中的任一种;所述有机钛酸酯类催化剂为钛酸异丙酯、钛酸丁酯中的任一种。
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