CN115260474A - 一种纸塑复合胶用聚酯及其制备方法与应用 - Google Patents
一种纸塑复合胶用聚酯及其制备方法与应用 Download PDFInfo
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Abstract
本发明提供了一种纸塑复合胶用聚酯,所述聚酯原料包括:醇、酸、酸酐、催化剂、助剂及填料,其中,所述醇、酸摩尔比为1.3‑1.8;所述醇的主链上C原子个数≤4,所述酸包括脂肪族酸和芳香族酸,所述脂肪族酸的主链上C原子个数≤5,所述芳香族酸的主链上C原子个数≤8;所述芳香族酸占酸的摩尔量20‑50%;采用本发明中的聚酯制得的纸塑复合胶与纸和PP/PET膜具有更强的附着力,提高酯键密度会提高复合胶与基材的附着力,由于酯键与基材会产生氢键的作用力;同时酯键在高湿碱性条件下易水解断裂,高酯键密度特性可以使得本发明制得的纸塑复合胶在水溶液中易与纸或塑料分离。
Description
技术领域
本发明属于胶黏剂技术领域,尤其涉及一种纸塑复合胶用聚酯及其制备方法与应用。
背景技术
复合包装材料是通过一些方法将两种或两种以上具有不同性能的材料结合而组成的包装材料,纸塑复合包装材料主要是纸类与塑料类基材之间进行的复合。随着人们环保意识的提升,已经成为食品包装的主流方式,但是由于其特殊的工艺,纸塑包装上的胶以及塑料膜无法回收利用,很容易造成资源的损失和环境的破坏。
为解决这一问题,目前采用的处理方法通常为:采用机械干分离的方法,将废弃纸塑包装进行物理切割粉碎,然后分级筛选将纸片和塑料片分开,该方法虽能够减少固体垃圾,可塑料和胶体部分依旧无法进一步回收,无法从根本上解决纸塑回收的问题。另一种是将纸塑包装清理后放置碱性溶液中,通过高温搅拌以及双氧水疏解,最终将纸塑分离,但工艺复杂,且需要高温条件,成本较高。专利申请CN113004858A中公开了一款纸塑复合胶,其以动物胶为原料,酶为催化剂,通过动物蛋白之间的交联形成网格状的分子链,从而提升胶体的黏性和耐温性,但其使用的是动物胶和酶催化剂,保存稳定性存在着较大的问题,难以工业化生产。
因此,需要开发一种复合胶,以从源头解决纸塑包装上的胶与塑料膜的分离,以有利于回收再利用,更好的符合环保要求。
发明内容
为了解决现有技术的不足,本发明提供了一种纸塑复合胶用聚酯及其制备方法与应用。
本发明的目的通过以下技术方案来实现:
一种纸塑复合胶用聚酯,所述聚酯原料包括:醇、酸、酸酐、催化剂、助剂及填料,其中,所述醇、酸摩尔比为1.3-1.8;所述醇的主链上C原子个数≤4,所述酸包括脂肪族酸和芳香族酸,所述脂肪族酸的主链上C原子个数≤5,所述芳香族酸的主链上C原子个数≤8;所述芳香族酸占酸的摩尔量20-50%;
所述聚酯的酯键酯键密度为(10.5-13)×10-3 mol/ml。
优选地,所述醇包括乙二醇、1,2-丙二醇、2-甲基-1,3-丙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇中的一种或一种以上组合。
优选地,所述酸包括对苯二甲酸、1,5-呋喃二甲酸、2,6-萘二甲酸二甲酯中的一种或一种以上。
优选地,所述酸还包括丙二酸二甲酯、丁二酸、戊二酸中的一种或一种以上组合。
优选地,所述酸酐包括偏苯三甲酸酐、均苯四甲酸酐、六氢苯酐中的一种或一种以上。
优选地,所述催化剂包括钛酸四丁酯、钛酸四乙酯、二丁基氧化锡、醋酸锌中的一种或一种以上。
优选地,所述助剂包括磷酸三甲酯、磷酸三乙酯、磷酸三丁酯中的一种或一种以上。
优选地,所述填料包括纳米氧化硅、纳米氧化铝、纳米氧化钛、纳米蒙脱土、纳米滑石粉、纳米黏土中的一种或一种以上。
优选地,以上任一所述的一种纸塑复合胶用聚酯的制备方法,包括如下步骤:S1、在不锈钢反应釜中,通入氮气保护,将酸、醇以及催化剂同时加入到反应釜中;
S2、维持反应体系常压下进行升温酯化,控制酯化率达到90%以上即停止;
S3、在氮气保护的情况下,向反应釜中加入助剂进行缩聚反应,真空度为小于100Pa,缩聚至整体物料羟值为30-40mgKOH/g时,降温;
S4、添加酸酐和纳米填料,维持S3温度下,进行常压搅拌,继续缩聚,维持缩聚温度,真空度小于300Pa,反应至合适粘度即可得到目标产物。
优选地,具有以上任一所述的一种纸塑复合胶用聚酯的复合胶,包括所述纸塑复合胶用聚酯、异氰酸酯固化剂、流平剂、润湿剂。
本发明的有益效果体现在:本发明中采用酯键密度为(10.5-13)×10-3 mol/ml的聚酯,使得制得的纸塑复合胶与纸和PP/PET膜具有更强的附着力,提高酯键密度会提高复合胶与基材的附着力,由于酯键与基材会产生氢键的作用力,同时酯键在高湿碱性条件下易水解断裂,高酯键密度特性可以使得本发明制得的纸塑复合胶在水溶液中易与纸或塑料分离,且本发明制得的复合胶生物降解性高,更符合环保要求。同时,体系中引进了具有对称性结构的芳香族酸,进一步提高了聚酯的结晶度和刚度,同时加入纳米填料,从而提高整体的水氧阻隔性。
具体实施方式
以下结合实施例具体阐述本发明的技术方案,本发明揭示了一种纸塑复合胶用聚酯及其制备方法与应用。
所述聚酯原料包括:醇、酸、酸酐、催化剂、助剂及填料,所述醇的主链上C原子个数≤4;所述酸包括脂肪族酸和芳香族酸,所述脂肪族酸的主链上C原子个数≤5,所述芳香族酸的主链上C原子个数≤8;所述芳香族酸占酸的摩尔量20-50%。
所述聚酯的制备方法包括如下步骤:
采用一步法投料,实施例中聚酯的醇酸摩尔比为1.3-1.8,在氮气保护的情况下,将所有单体催化剂一起投进不锈钢反应釜中,常压反应,搅拌速率为60-100r/min,按照0.5℃/min的速率进行升温酯化,最高温度达到220-240℃,样品的酯化率达到90%以上即为酯化结束,得到酯化产物;
在酯化产物中添加助剂,维持220-280℃缩聚,搅拌速率为40-100r/min,真空度小于100Pa,缩聚至整体物料羟值为30-40mgKOH/g时,降温至220℃,添加酸酐和填料,维持220±5℃,常压搅拌30min,后继续缩聚,维持缩聚温度220-240℃,搅拌速率为60-80r/min,真空度小于300Pa,反应至合适粘度即可得到目标产物。
本发明列举了8个实施例,以及3个对比例,涉及的组分、投料量以及工艺参数具体参见以下表1-表5:
投料配方表
表1:酸类投料表:
实验编号 | 对苯二甲酸 | 2,6-萘二甲酸二甲酯 | 1,5-呋喃二甲酸 | 丙二酸二甲酯 | 丁二酸 | 戊二酸 | 十二烷二酸 |
实施例1 | 160.41 | 235.83 | 150.72 | 255.13 | / | / | / |
实施例2 | / | 233.91 | 149.49 | / | 169.64 | 189.80 | / |
实施例3 | 242.05 | 118.62 | / | / | 344.11 | / | / |
实施例4 | 34.32 | 252.28 | 193.48 | / | / | 218.35 | / |
实施例5 | 81.42 | 119.70 | 229.49 | 194.24 | 115.75 | / | / |
实施例6 | 103.29 | 303.71 | 97.05 | 109.52 | / | 109.53 | / |
实施例7 | 36.58 | 161.33 | 137.47 | 116.35 | 104.01 | 116.36 | / |
实施例8 | 165.78 | / | 233.64 | 65.92 | 235.68 | / | / |
对比例1 | 144.70 | 372.29 | 135.96 | 86.30 | 51.43 | / | / |
对比例2 | 117.43 | 172.64 | 110.33 | / | / | / | 322.72 |
对比例3 | 115.7 | / | 108.71 | 214.68 | / | 214.70 | / |
表2:醇类投料表:
实验编号 | 乙二醇 | 新戊二醇 | 1,2-丙二醇 | 1,3-丙二醇 | 1,4-丁二醇 | 2-甲基-1,3-丙二醇 | 1,6-己二醇 |
实施例1 | 149.83 | 201.13 | / | 146.94 | / | / | / |
实施例2 | 148.61 | 149.62 | / | / | 172.62 | 86.31 | / |
实施例3 | 180.87 | 303.49 | 110.86 | / | / | / | / |
实施例4 | 51.29 | 344.26 | / | 94.31 | 111.71 | / | / |
实施例5 | 212.94 | 153.13 | 74.58 | 74.58 | 44.17 | / | / |
实施例6 | 128.64 | 172.68 | / | 126.16 | 149.42 | / | / |
实施例7 | 218.67 | 91.73 | / | / | / | 317.49 | / |
实施例8 | 170.33 | 51.97 | 151.86 | / | / | 224.82 | / |
对比例1 | 162.19 | 181.43 | 66.28 | 99.41 | / | / | / |
对比例2 | 43.87 | 73.62 | / | / | / | / | 459.39 |
对比例3 | 144.09 | 193.43 | / | 141.31 | 167.37 | / | / |
表3:酸酐和填料投料表:
实验编号 | 偏苯三酸酐 | 均苯四甲酸酐 | 六氢苯酐 | 纳米蒙脱土 | 纳米滑石粉 | 纳米氧化铝 | 纳米氧化硅 |
实施例1 | 20.00 | / | / | 20.00 | / | / | / |
实施例2 | / | 22.71 | / | / | / | 20.00 | / |
实施例3 | / | / | 16.05 | / | 20.00 | / | / |
实施例4 | 10.00 | 11.35 | / | / | / | / | 20.00 |
实施例5 | 10.00 | / | 8.02 | 10.00 | / | 10.00 | / |
实施例6 | / | 11.35 | 8.02 | / | 10.00 | / | 10.00 |
实施例7 | 5.00 | 17.03 | / | 5.00 | 10.00 | / | 5.00 |
实施例8 | 15.00 | 5.68 | / | 10.00 | / | 5.00 | 5.00 |
对比例1 | 20.00 | / | / | 20.00 | / | / | / |
对比例2 | 20.00 | / | / | 20.00 | / | / | / |
对比例3 | / | 11.35 | 8.02 | / | 10.00 | / | 10.00 |
表4:催化剂和助剂投料表:
实验编号 | 钛酸四丁酯 | 钛酸四乙酯 | 二丁基氧化锡 | 醋酸锌 | 磷酸三甲酯 | 磷酸三乙酯 | 磷酸三丁酯 |
实施例1 | 0.10 | / | / | 0.03 | 0.06 | / | / |
实施例2 | / | 0.10 | / | 0.03 | / | 0.06 | / |
实施例3 | 0.06 | / | 0.07 | / | / | / | 0.06 |
实施例4 | 0.06 | / | / | 0.07 | / | 0.06 | / |
实施例5 | / | 0.06 | 0.07 | / | 0.03 | / | 0.03 |
实施例6 | 0.04 | / | 0.09 | / | 0.03 | 0.03 | / |
实施例7 | / | 0.04 | 0.09 | / | 0.03 | 0.03 | |
实施例8 | / | 0.04 | 0.09 | / | 0.02 | / | 0.04 |
对比例1 | 0.10 | / | / | 0.03 | 0.06 | / | / |
对比例2 | 0.10 | / | / | 0.03 | 0.06 | / | / |
对比例3 | 0.04 | / | 0.09 | / | 0.03 | 0.03 | / |
表5:样品工艺控制表:
实验编号 | 酯化温度 | 酯化转速 | 缩聚温度 | 缩聚转速 | 酸化后温度 | 酸化后转速 |
实施例1 | 240.00 | 100.00 | 280.00 | 100.00 | 235.00 | 80.00 |
实施例2 | 235.00 | 90.00 | 260.00 | 80.00 | 220.00 | 60.00 |
实施例3 | 240.00 | 100.00 | 230.00 | 60.00 | 240.00 | 80.00 |
实施例4 | 225.00 | 60.00 | 240.00 | 40.00 | 225.00 | 70.00 |
实施例5 | 235.00 | 70.00 | 250.00 | 60.00 | 235.00 | 80.00 |
实施例6 | 240.00 | 100.00 | 270.00 | 100.00 | 225.00 | 70.00 |
实施例7 | 230.00 | 80.00 | 240.00 | 90.00 | 220.00 | 60.00 |
实施例8 | 220.00 | 60.00 | 220.00 | 70.00 | 230.00 | 70.00 |
对比例1 | 240.00 | 100.00 | 280.00 | 100.00 | 235.00 | 80.00 |
对比例2 | 240.00 | 100.00 | 280.00 | 100.00 | 235.00 | 80.00 |
对比例3 | 240.00 | 100.00 | 270.00 | 100.00 | 225.00 | 70.00 |
将实施例1-8和对比例1-3所得到的样品,采用常规水性共聚酯溶解工艺进行溶解,助剂含量为5-15%,从而得到固含30-45%,粒径分布为600-800nm的乳白色液体,加入异氰酸酯固化剂,流平剂,润湿剂,搅拌混合均匀即可制得复合胶。采用线棒法,将胶黏剂均匀的涂布在纸张上,放入95℃烘箱内烘3min后,用PET膜均匀粘贴在涂胶的一面上,室温放置24h。
理化测试:
将实施例1-8和对比例1-3得到的样品制得的复合胶进行性能表征。
特性粘度是使用乌氏粘度计,采用邻氯苯酚作为溶剂,在温度35℃条件下测得。
玻璃化转变温度测试采用美国TA Q20差示扫描量热仪,测试时氮气气氛下的流速为20mL/min,5mg的样品被放置在一个氧化铝样品盘,测试过程如下:样品以10℃/min的升温速率从-30℃被加热到180℃,在此状态下保持2min消除热历史,样品以10℃/min的降温速率冷却到-30℃。随后,样品经历二次升温过程,从-30℃以10℃/min的升温速率升到150℃,样品的玻璃化转变温度(Tg)由二次升温获得。
水透过性:GB/T 26253-2010《塑料薄膜和薄片水蒸气透过率的测定红外检测器法》其中,塑料层面面向水蒸气。
氧透过性:GB/T19789-2005《包装材料塑料薄膜和薄片氧气透过性实验库仑计检测法》。
生物可降解率实验结果有效性判定:
1)参考国标:GB/T 19277.1-2011《受控堆肥条件下材料最终需氧生物分解能力的测定采用测定释放的二氧化碳的方法第1部分:通用方法》
2)在测试第45天参比材料(TLC级纤维素)的生物降解百分率>70%。
3)在实验结束时,每个堆肥容器的生物分解百分率之间的最大相对偏差<20%。
试验前10天内,空白组中接种物产生的二氧化碳平均值为在50~150 mg CO2/g挥发性固体(平均值)范围内。
纸塑剥离强度参考GB/T 2792-2014《胶粘带剥离强度的试验方法》,将制得的样条,在纸质背面粘贴一层3M胶,以提高纸张强度,避免测试过程中断裂,进行180°剥离强度测试。采用恒速拉伸试验机,自动记录至少每剥离1mm膜材记录一个数值。试验机配备两种夹具校准(在同一中心线上),平行对位,在移动方向上处于同一平面内。整幅夹紧试样,以(5.0±0.2)mm/s的匀速速度移动,记录载荷读数。最大允许误差为2%。
可剥离性测试
将复合后的纸塑膜切片,切成4×8cm的条状,放置于0.1wt%NaOH水溶液中,浸渍30min,采用机械搅拌30s,转速为60r/min,通过肉眼评判其可剥离性。
纸塑分离,且纸质材料以及PP/PET膜上无残留胶表示“优”;
纸塑分离,纸质材料以及PP/PET膜上有部分残留胶表示“良”;
纸塑分离不彻底表示“差”。
以上性能测试结果如下表所示:
表6:各实施例的性能测试结果表:
分析上表数据可知,采用本发明的酯键密度为(10.5-13)×10-3 mol/ml的聚酯制得的复合胶在透氧量和透水量上均有着优异的表现,且生物降解率高,可剥离性强。相应的,若酯键密度过高或过低,则最终制得的复合胶的透氧量或生物降解率、可剥离性上会有不同程度的影响。
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解: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;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种纸塑复合胶用聚酯,其特征在于:所述聚酯原料包括:醇、酸、酸酐、催化剂、助剂及填料,其中,所述醇、酸摩尔比为1.3-1.8;所述醇的主链上C原子个数≤4,所述酸包括脂肪族酸和芳香族酸,所述脂肪族酸的主链上C原子个数≤5,所述芳香族酸的主链上C原子个数≤8;所述芳香族酸占酸的摩尔量20-50%;
所述聚酯酯键密度为(10.5-13)×10-3 mol/ml。
2.如权利要求1所述的一种纸塑复合胶用聚酯,其特征在于:所述醇包括乙二醇、1,2-丙二醇、2-甲基-1,3-丙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇中的一种或一种以上组合。
3.如权利要求1所述的一种纸塑复合胶用聚酯,其特征在于:所述酸包括对苯二甲酸、1,5-呋喃二甲酸、2,6-萘二甲酸二甲酯中的一种或一种以上组合。
4.如权利要求3所述的一种纸塑复合胶用聚酯,其特征在于:所述酸还包括丙二酸二甲酯、丁二酸、戊二酸中的一种或一种以上组合。
5.如权利要求1所述的一种纸塑复合胶用聚酯,其特征在于:所述酸酐包括偏苯三甲酸酐、均苯四甲酸酐、六氢苯酐中的一种或一种以上。
6.如权利要求1所述的一种纸塑复合胶用聚酯,其特征在于:所述催化剂包括钛酸四丁酯、钛酸四乙酯、二丁基氧化锡、醋酸锌中的一种或一种以上。
7.如权利要求1所述的一种纸塑复合胶用聚酯,其特征在于:所述助剂包括磷酸三甲酯、磷酸三乙酯、磷酸三丁酯中的一种或一种以上。
8.如权利要求1所述的一种纸塑复合胶用聚酯,其特征在于:所述填料包括纳米氧化硅、纳米氧化铝、纳米氧化钛、纳米蒙脱土、纳米滑石粉、纳米黏土中的一种或一种以上。
9.如权利要求1-8中任一所述的一种纸塑复合胶用聚酯的制备方法,其特征在于:包括如下步骤:
S1、在不锈钢反应釜中,通入氮气保护,将酸、醇以及催化剂同时加入到反应釜中;
S2、维持反应体系常压下进行升温酯化,控制酯化率达到90%以上即停止;
S3、在氮气保护的情况下,向反应釜中加入助剂进行缩聚反应,真空度为小于100Pa,缩聚至整体物料羟值为30-40mgKOH/g时,降温;
S4、添加酸酐和纳米填料,维持S3温度下,进行常压搅拌,继续缩聚,维持缩聚温度,真空度小于300Pa,反应至合适粘度即可得到目标产物。
10.具有如权利要求1-8中任一所述的一种纸塑复合胶用聚酯的复合胶,其特征在于:包括所述纸塑复合胶用聚酯、异氰酸酯固化剂、流平剂、润湿剂。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002371259A (ja) * | 2001-06-15 | 2002-12-26 | Showa Highpolymer Co Ltd | 生分解性水分散系接着剤組成物 |
US20060247326A1 (en) * | 2003-09-25 | 2006-11-02 | Guenter Henke | Adhesive composition with barrier characteristics |
CN105602491A (zh) * | 2016-01-30 | 2016-05-25 | 常州市庆发工业气体有限公司 | 一种易脱除纸塑复合胶的制备方法 |
CN109293904A (zh) * | 2018-09-03 | 2019-02-01 | 杭州福斯特应用材料股份有限公司 | 一种高耐候性聚酯树脂及用途 |
CN110253997A (zh) * | 2019-06-03 | 2019-09-20 | 睿泊(中国)环保科技有限公司 | 一种可分类回收金属、塑料、纸的环保型复合材料及其制备方法 |
CN113307956A (zh) * | 2020-02-27 | 2021-08-27 | 中国科学院理化技术研究所 | 一种可降解的共聚酯及其制备方法和应用 |
CN113354799A (zh) * | 2021-04-26 | 2021-09-07 | 浙江恒澜科技有限公司 | 一种长链支化可降解聚酯及其制备方法 |
-
2022
- 2022-08-26 CN CN202211030230.3A patent/CN115260474A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002371259A (ja) * | 2001-06-15 | 2002-12-26 | Showa Highpolymer Co Ltd | 生分解性水分散系接着剤組成物 |
US20060247326A1 (en) * | 2003-09-25 | 2006-11-02 | Guenter Henke | Adhesive composition with barrier characteristics |
CN105602491A (zh) * | 2016-01-30 | 2016-05-25 | 常州市庆发工业气体有限公司 | 一种易脱除纸塑复合胶的制备方法 |
CN109293904A (zh) * | 2018-09-03 | 2019-02-01 | 杭州福斯特应用材料股份有限公司 | 一种高耐候性聚酯树脂及用途 |
CN110253997A (zh) * | 2019-06-03 | 2019-09-20 | 睿泊(中国)环保科技有限公司 | 一种可分类回收金属、塑料、纸的环保型复合材料及其制备方法 |
CN113307956A (zh) * | 2020-02-27 | 2021-08-27 | 中国科学院理化技术研究所 | 一种可降解的共聚酯及其制备方法和应用 |
CN113354799A (zh) * | 2021-04-26 | 2021-09-07 | 浙江恒澜科技有限公司 | 一种长链支化可降解聚酯及其制备方法 |
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