CN111171275B - 一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法与应用 - Google Patents
一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法与应用。所述聚氨酯材料由100重量份低聚物多元醇、1.5~7重量份碱处理的竹纤维、20~45重量份2,4‑甲苯二异氰酸酯、10~26重量份胺类扩链剂和0.3~1.2重量份不饱和脂肪酸制备而成。本发明制得的聚氨酯材料通过旋转浇注工艺浇注到管道内壁,厚度均匀,粘接牢固,固化后不变形,不影响管端间链接,耐磨性能好,输送管使用寿命长。
Description
技术领域
本发明属于聚氨酯弹性体技术领域,具体涉及一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法与应用。
背景技术
采沙行业主要采用金属管道输送沙子,由于沙水的冲蚀,金属管道内壁容易被磨损从而影响使用寿命。这种情况下,高分子材料/金属复合管道应运而生。目前应用较好的内衬材料是超高分子量聚乙烯,采用先挤出预制内衬管,然后将预制的内衬套进金属管的方式制备。但超高分子量聚乙烯内衬材料蠕变较大,影响到管端连接,导致运输中沙水泄露。
聚氨酯弹性体具有硬度范围宽,耐磨性能好,容易与金属粘接等特点。内衬聚氨酯通过旋转浇注工艺均匀、牢固涂覆在金属管道内壁,能极大缓解管道内壁所受冲击。因此聚氨酯内衬管道具有很好的应用前景。
发明内容
为解决现有技术的缺点和不足之处,本发明的首要目的在于提供一种耐沙水磨损的管道内衬用聚氨酯材料。所述聚氨酯材料耐磨性能好、使用寿命长,适用于沙水输送管道内衬。
本发明的另一目的在于提供上述一种耐沙水磨损的管道内衬用聚氨酯材料的制备方法。
本发明的再一目的在于提供上述一种耐沙水磨损的管道内衬用聚氨酯材料的应用。
本发明目的通过以下技术方案实现:
一种耐沙水磨损的管道内衬用聚氨酯材料,由如下组分制备而成:
所述碱处理的竹纤维的纤维素质量含量在70%以上,尺寸在30~100目之间。
优选的,所述耐沙水磨损的管道内衬用聚氨酯材料,由如下组分制备而成:
优选的,所述低聚物多元醇为分子量为650~2000的聚四氢呋喃二醇与聚已二酸乙二醇酯的混合物,其中聚四氢呋喃二醇占混合物质量的70~90%。
优选的,所述胺类扩链剂为4,4'-二氨基-3,3'-二氯二苯甲烷和2,4-二氨基-3,5-二甲硫基甲苯中的至少一种。
优选的,所述不饱和脂肪酸的主链碳原子数在15~20之间;更优选为十六碳烯酸和十八碳烯酸中的至少一种。
上述一种耐沙水磨损的管道内衬用聚氨酯材料的制备方法,包括以下步骤:
(1)将100重量份竹纤维浸入氢氧化钠溶液中,在80~110℃下浸泡1~3小时,水洗,干燥,破碎至30~100目,得到碱处理的竹纤维;
(2)将1.5~7重量份步骤(1)的竹纤维、0.3~1.2重量份不饱和脂肪酸和100重量份低聚物多元醇加热脱水处理,降温至50~60℃,所得混合物滴加到30~40℃、20~45重量份2,4-甲苯二异氰酸酯中,35~90分钟滴加完毕,在60~70℃下反应1~2小时,然后升温至85~90℃继续反应2~3小时,得到聚氨酯预聚体;
(3)将步骤(2)的聚氨酯预聚体加热至80~90℃,在真空度≤500Pa下脱泡15~30分钟,加入10~26重量份胺类扩链剂,混合均匀,然后倒入预先涂好脱模剂的模具中,在60~100℃下固化2~4小时,得到聚氨酯弹性体材料。
优选的,步骤(1)所述氢氧化钠溶液为1500~2500重量份,其质量浓度为10~20%。
优选的,步骤(1)所述水洗指将所得产物水洗至中性。
优选的,步骤(1)所述干燥的温度为100~120℃,时间为6~8小时。
优选的,步骤(1)所述浸泡的温度为85~95℃。
优选的,步骤(2)所述加热脱水处理的条件为:在120~130℃以及真空度≤500Pa下脱水2~3小时。
优选的,步骤(3)所述固化温度为65~95℃。
上述一种耐沙水磨损的管道内衬用聚氨酯材料的应用。
优选的,所述应用为在运沙管道内衬材料领域中的应用。
本发明所述聚氨酯材料配方体系中,占多元醇10~30%质量份的聚已二酸乙二醇酯能有效降低聚氨酯预聚体的粘度,使预聚体可以适应于旋转浇注工艺。高纤维素含量的竹纤维可改善聚氨酯材料的拉伸强度和撕裂强度,从而提高聚氨酯材料的抗沙水磨损性能。不饱和酸可以提高扩链剂与预聚体的反应活性,使固化反应可以在较低温度、较短时间内完成,提高生产效率,降低生产成本。
与现有技术相比,本发明具有以下优点及有益效果:
(1)本发明所述聚氨酯通过旋转浇注工艺浇注到管道内壁,厚度均匀,粘接牢固。
(2)本发明所述聚氨酯固化后不变形,不影响管端间连接。
(3)本发明所述聚氨酯材料耐磨性能好,输送管使用寿命长。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
本发明实施例中未注明具体条件者,按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等,均为可以通过市售购买获得的常规产品。
本申请实施例和对比例中步骤(1)所得碱处理的竹纤维纤维素质量含量均在70%以上。
实施例1
一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法,包括以下步骤:
(1)竹纤维的制备:将100重量份的竹纤维(福建海博斯化学技术有限公司竹原纤维)浸入1500重量份质量浓度为12.5%的氢氧化钠溶液中,85℃下浸泡3小时,取出竹纤维,用水洗至pH值为中性。然后置于105℃烘箱中干燥8小时,用中药破碎机将竹纤维破碎至尺寸为30~50目待用。
(2)聚氨酯预聚体的制备:称取步骤(1)制备的竹纤维6.5重量份,十六碳烯酸(天津科密欧化学试剂有限公司)1.1重量份,分子量为2000的聚四氢呋喃二醇(牌号PTMG2000)90重量份,分子量为1000的聚己二酸乙二醇酯(牌号PE-2010,山东一诺威聚氨酯股份有限公司)10重量份,加入到配有搅拌器、真空系统和温度计的反应釜中,混合均匀。将反应物加热至120℃,抽真空至余压小于500Pa,脱水3小时,然后降温至55℃;将反应物缓慢滴加到35℃、20重量份的2,4-甲苯二异氰酸酯(Desmodur T100)中,35分钟滴加完毕,使反应混合物体系的温度保持在65℃;滴加完后保温1小时,然后升温至90℃反应2小时,得到聚氨酯预聚体。
(3)聚氨酯弹性体的制备:将步骤(2)制备的聚氨酯预聚体,加热至90℃,抽真空至余压小于500Pa,脱泡30分钟;加入2,4-二氨基-3,5-二甲硫基甲苯(淄博方中化工有限公司)10.8重量份,快速混合均匀,然后倒入预先涂好脱模剂的模具中,放入65℃烘箱中,后处理4小时即成为聚氨酯弹性体。
实施例2
一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法,包括以下步骤:
(1)竹纤维的制备:将100重量份的竹纤维(福建海博斯化学技术有限公司竹原纤维)浸入2000重量份质量浓度为15%的氢氧化钠溶液中,95℃下浸泡2小时,取出竹纤维,用水洗至pH值为中性。然后置于110℃烘箱干燥7小时,用中药破碎机将竹纤维破碎至尺寸为60~80目待用。
(2)聚氨酯预聚体的制备:称取步骤(1)制备的竹纤维3.5重量份,十八碳烯酸(天津科密欧化学试剂有限公司)0.9重量份,分子量为1000的聚四氢呋喃二醇(牌号PTMG2000)80重量份,分子量为1000的聚己二酸乙二醇酯(牌号PE-2010,山东一诺威聚氨酯股份有限公司)20重量份,加入到配有搅拌器、真空系统和温度计的反应釜中,混合均匀。将反应物加热至125℃,抽真空至余压小于500Pa,脱水2.5小时,然后降温至58℃;将反应物缓慢滴加到40℃、35重量份的2,4-甲苯二异氰酸酯(Desmodur T100)中,75分钟滴加完毕,使反应混合物体系的温度保持在70℃;滴加完后保温1.5小时,然后升温至85℃反应3小时,得到聚氨酯预聚体。
(3)聚氨酯弹性体的制备:将步骤(2)制备的聚氨酯预聚体,加热至85℃,抽真空至余压小于500Pa,脱泡20分钟;加入4,4'-二氨基-3,3'-二氯二苯甲烷(苏州湘园新材料股份有限公司)25.3重量份,快速混合均匀,然后倒入预先涂好脱模剂的模具中,放入90℃烘箱中,后处理2.5小时即成为聚氨酯弹性体。
实施例3
一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法,包括以下步骤:
(1)竹纤维的制备:将100重量份的竹纤维(福建海博斯化学技术有限公司竹原纤维)浸入2500重量份质量浓度为20%的氢氧化钠溶液中,105℃下浸泡1小时,取出竹纤维,用水洗至pH值为中性。然后置于115℃烘箱干燥6小时,用中药破碎机将竹纤维破碎至尺寸为80~100目待用。
(2)聚氨酯预聚体的制备:称取步骤(1)制备的竹纤维2.0重量份,十六碳烯酸(天津科密欧化学试剂有限公司)0.5重量份,分子量为650的聚四氢呋喃二醇(牌号PTMG2000)70重量份,分子量为1000的聚己二酸乙二醇酯(牌号PE-2010,山东一诺威聚氨酯股份有限公司)30重量份,加入到配有搅拌器、真空系统和温度计的反应釜中,混合均匀。将反应物加热至130℃,抽真空至余压小于500Pa,脱水2小时,然后降温至55℃;将反应物缓慢滴加到38℃、44重量份的2,4-甲苯二异氰酸酯(Desmodur T100)中,90分钟滴加完毕。滴加完后保温1.5小时,然后升温至87℃反应2.5小时,得到聚氨酯预聚体。
(3)聚氨酯弹性体的制备:将步骤(2)制备的聚氨酯预聚体,加热至85℃,抽真空至余压小于500Pa,脱泡15分钟;加入2,4-二氨基-3,5-二甲硫基甲苯(淄博方中化工有限公司)22.7重量份,快速混合均匀,然后倒入预先涂好脱模剂的模具中,放入95℃烘箱中,后处理2小时即成为聚氨酯弹性体。
对比例1
一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法,包括以下步骤:
(1)竹纤维的制备:将竹纤维(福建海博斯化学技术有限公司竹原纤维)用中药破碎机将竹纤维破碎至尺寸为30~50目待用。
(2)聚氨酯预聚体的制备:称取步骤(1)制备的竹纤维6.5重量份,十六碳烯酸(天津科密欧化学试剂有限公司)1.1重量份,分子量为2000的聚四氢呋喃二醇(牌号PTMG2000)90重量份,分子量为1000的聚己二酸乙二醇酯(牌号PE-2010,山东一诺威聚氨酯股份有限公司)10重量份,加入到配有搅拌器、真空系统和温度计的反应釜中,混合均匀。将反应物加热至120℃,抽真空至余压小于500Pa,脱水3小时,然后降温至55℃;将反应物缓慢滴加到35℃、20重量份的2,4-甲苯二异氰酸酯(Desmodur T100)中,35分钟滴加完毕,使反应混合物体系的温度保持在65℃;滴加完后保温1小时,然后升温至90℃反应2小时,得到聚氨酯预聚体。
(3)聚氨酯弹性体的制备:将步骤(2)制备的聚氨酯预聚体,加热至90℃,抽真空至余压小于500Pa,脱泡30分钟;加入2,4-二氨基-3,5-二甲硫基甲苯(淄博方中化工有限公司)10.8重量份,快速混合均匀,然后倒入预先涂好脱模剂的模具中,放入65℃烘箱中,后处理4小时即成为聚氨酯弹性体。
对比例2
一种耐沙水磨损的管道内衬用聚氨酯材料及其制备方法,包括以下步骤:
(1)竹纤维的制备:将100重量份的竹纤维(福建海博斯化学技术有限公司竹原纤维)浸入1500重量份质量浓度为12.5%的氢氧化钠溶液中,85℃下浸泡3小时,取出竹纤维,用水洗至pH值为中性。然后置于105℃烘箱中干燥8小时,用中药破碎机将竹纤维破碎至尺寸为30~50目待用。
(2)聚氨酯预聚体的制备:称取步骤(1)制备的竹纤维10重量份,十六碳烯酸(天津科密欧化学试剂有限公司)1.1重量份,分子量为2000的聚四氢呋喃二醇(牌号PTMG2000)90重量份,分子量为1000的聚己二酸乙二醇酯(牌号PE-2010,山东一诺威聚氨酯股份有限公司)10重量份,加入到配有搅拌器、真空系统和温度计的反应釜中,混合均匀。将反应物加热至120℃,抽真空至余压小于500Pa,脱水3小时,然后降温至55℃;将反应物缓慢滴加到35℃、20重量份的2,4-甲苯二异氰酸酯(Desmodur T100)中,35分钟滴加完毕,使反应混合物体系的温度保持在65℃;滴加完后保温1小时,然后升温至90℃反应2小时,得到聚氨酯预聚体。
(3)聚氨酯弹性体的制备:将步骤(2)制备的聚氨酯预聚体,加热至90℃,抽真空至余压小于500Pa,脱泡30分钟;加入2,4-二氨基-3,5-二甲硫基甲苯(淄博方中化工有限公司)10.8重量份,快速混合均匀,然后倒入预先涂好脱模剂的模具中,放入65℃烘箱中,后处理4小时即成为聚氨酯弹性体。
实施例1~3和对比例1~2所制得的聚氨酯弹性体的具体效果见表1:
表1聚氨酯管道内衬与超高分子量聚乙烯内衬性能对比
*自制设备,采用20L机油桶,装沙5L,装水6L;电机30Hz(840RPM),实验时间:72Hr(小时)。试验方法:将试样称重,固定到试样夹持器上,夹持器通过减速箱与电机连接,将夹持器放进沙水桶中,试样完全被沙水淹没;启动电机,夹持器带动试样在沙水中连续持续转动,承受沙水冲击磨损,72Hr后取下试样,将表面清洗干净,烘干后称重。磨损量为试样试验前后的重量差。
从表1可以看出:本专利制备的聚氨酯材料的耐沙水磨损性能优于45#钢;与超高分子量聚乙烯相比,本专利制备的氨酯弹性体强度高,扯断伸长率大,表现出更好的延伸性能;抗曲挠性能好;抗沙水磨损性能好,管道使用寿命长。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种耐沙水磨损的管道内衬用聚氨酯材料的制备方法,其特征在于,包括以下步骤:
(1)将100重量份竹纤维浸入氢氧化钠溶液中,在80~110℃下浸泡1~3小时,水洗,干燥,破碎至30~100目,得到碱处理的竹纤维;
(2)将1.5~7重量份步骤(1)的竹纤维、0.3~1.2重量份不饱和脂肪酸和100重量份低聚物多元醇加热脱水处理,降温至50~60℃,所得混合物滴加到30~40℃、20~45重量份2,4-甲苯二异氰酸酯中,35~90分钟滴加完毕,在60~70℃下反应1~2小时,然后升温至85~90℃继续反应2~3小时,得到聚氨酯预聚体;
(3)将步骤(2)的聚氨酯预聚体加热至80~90℃,在真空度≤500Pa下脱泡15~30分钟,加入10~26重量份胺类扩链剂,混合均匀,然后倒入预先涂好脱模剂的模具中,在60~100℃下固化2~4小时,得到聚氨酯弹性体材料;
步骤(1)所得碱处理的竹纤维的纤维素质量含量在70%以上,尺寸在30~100目之间;
步骤(2)所述低聚物多元醇为分子量为650~2000的聚四氢呋喃二醇与聚已二酸乙二醇酯的混合物,其中聚四氢呋喃二醇占混合物质量的70~90%;所述不饱和脂肪酸的主链碳原子数在15~20之间。
2.根据权利要求1所述一种耐沙水磨损的管道内衬用聚氨酯材料的制备方法,其特征在于,步骤(1)所述氢氧化钠溶液为1500~2500重量份,其质量浓度为10~20%,步骤(2)所述加热脱水处理的条件为:在120~130℃以及真空度≤500Pa下脱水2~3小时。
3.根据权利要求1或2所述一种耐沙水磨损的管道内衬用聚氨酯材料的制备方法,其特征在于,步骤(1)所述干燥的温度为100~120℃,时间为6~8小时;所述浸泡的温度为85~95℃;
步骤(3)所述固化温度为65~95℃。
4.根据权利要求1所述一种耐沙水磨损的管道内衬用聚氨酯材料的制备方法,其特征在于,所述胺类扩链剂为4,4'-二氨基-3,3'-二氯二苯甲烷和2,4-二氨基-3,5-二甲硫基甲苯中的至少一种。
5.根据权利要求1所述一种耐沙水磨损的管道内衬用聚氨酯材料的制备方法,其特征在于,所述不饱和脂肪酸为十六碳烯酸和十八碳烯酸中的至少一种。
6.权利要求1~5任一项所述方法制得的一种耐沙水磨损的管道内衬用聚氨酯材料。
7.权利要求6所述一种耐沙水磨损的管道内衬用聚氨酯材料在运沙管道内衬材料领域中的应用。
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