CN117545789A - 基于聚氨酯的热熔粘合剂 - Google Patents
基于聚氨酯的热熔粘合剂 Download PDFInfo
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- CN117545789A CN117545789A CN202280043828.8A CN202280043828A CN117545789A CN 117545789 A CN117545789 A CN 117545789A CN 202280043828 A CN202280043828 A CN 202280043828A CN 117545789 A CN117545789 A CN 117545789A
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- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 claims description 3
- WGTGQGJDNAGBCC-UHFFFAOYSA-N hex-5-ene-1,2-diol Chemical compound OCC(O)CCC=C WGTGQGJDNAGBCC-UHFFFAOYSA-N 0.000 claims description 3
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- UXGHWJFURBQKCJ-UHFFFAOYSA-N oct-7-ene-1,2-diol Chemical compound OCC(O)CCCCC=C UXGHWJFURBQKCJ-UHFFFAOYSA-N 0.000 claims description 3
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
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- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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Abstract
热熔粘合剂,其包含无规羟基官能化的分支烯烃共聚物,所述共聚物具有:10至50kg/mol、优选20至50kg/mol的数均分子量(Mn),低于30%、优选低于15%、更优选低于10%的结晶度(Xc)含量,5至65J/g、优选5至30J/g的焓(ΔH),2至6、优选严格地大于3且小于6的多分散性指数(PDI),40至120℃的熔化温度(Tm),任选地,每条聚合物链多于两个羟基官能团;并且由以下组成:至少80mol%的由式(1)表示的组成单元,任选的由式(2)表示的组成单元,和0.1至1mol%、优选0.1至0.5mol%的由式(3)表示的组成单元;其中:R1为H或CH3;R2选自包含以下的列表:具有0至10个,在R1=H时优选2至6个且更优选6个,且在R1=CH3时优选0、2或4个碳原子的烃基;R3为具有2至10、优选2至8、优选4至8、更优选4或6个碳原子的烃基;且其中所述羟基官能化烯烃共聚物已经历了与由式(4)表示的二、三或多异氰酸酯的加成反应;其中,R4为具有1至10个碳原子的烃基,并且n为1至4、优选1至2、更优选1。
Description
技术领域
本发明涉及基于聚氨酯的热熔粘合剂。
背景技术
热熔粘合剂(HMA)也称为热熔胶,是在环境温度下为固态并且可熔化以将其施用于表面上的热塑性粘合树脂。最常见用作HMA的是EVA或聚烯烃弹性体。其它实例是热塑性聚氨酯(TPU)、苯乙烯嵌段共聚物(SBC)、聚酰胺或聚酯。
HMA可以数种形式诸如棒、粒料、珠、颗粒、锭、片、栓、飞片、垫、块、膜或喷雾应用,并且用于各种应用如包装、卫生用品、家具、鞋类、织物和皮革、电子、书籍装订和制图、建筑与施工、消费者DIY中。
HMA相较于溶剂基粘合剂提供几个优点。减少或消除了挥发性有机化合物,并且消除了二组分粘合剂通常所需的干燥或固化步骤。此外,HMA通常具有高里程、低气味且是热稳定的。HMA具有长保存期并且通常可无需特殊预防措施而处置。此外,因为是热塑塑料,可通过加热基材来简单地逆转HMA粘合。这种可逆粘合的明显缺陷是在较高温度下丧失粘合强度,直至粘合剂完全熔化。因此,HMA的使用限于不暴露于高温的应用。
基于聚烯烃的HMA对低表面能材料、诸如未处理的聚烯烃显示出良好的粘附,或它们可被施用于诸如纸、纸板或木材的多孔材料,其中粘附是通过使HMA物理包含于多孔材料中获得的。然而,这些基于聚烯烃的HMA通常对诸如金属、玻璃和极性聚合材料的极性材料显示出低粘合强度。
EP1186619公开了在基于聚烯烃的HMA中使用具有多于13个碳C13以上的极性官能化单体以改进对极性基材诸如聚碳酸酯和铝的粘附。
然而,含有这种官能化单体的HMA具有有限的粘合强度。
聚氨酯因其展现高性能和通用性而是优异的聚合物,这使它们被用于各种各样的工业和工程应用、包括粘合剂。聚氨酯通常通过二、三或多异氰酸酯与通常为低分子量聚醚、聚酯或聚丁二烯的增链剂的羟基反应来产生。已知异氰酸酯粘合剂的耐久性强烈依赖水的存在,因为水加速接合的降解。
本发明的目的在于提供包含含极性基团的烯烃共聚物的热熔粘合剂,其对金属或极性树脂和非极性树脂具有优异的粘附性质。
需要新的热熔粘合剂,其具有根据ASTM D1002-10(2019)利用配备有10kN载荷传感器的Zwick Z020型拉伸试验机测量的以下粘合性质中的至少一者:
·3MPa以上、优选4MPa以上、更优选5MPa以上、甚至更优选9MPa以上的钢与钢的搭接剪切强度,
·3MPa以上、优选4MPa以上、更优选5MPa以上的铝与铝的搭接剪切强度,
·3MPa以上、优选4MPa以上、更优选5MPa以上的聚烯烃与聚烯烃的搭接剪切强度。
发明内容
这一目的通过本发明的包含无规羟基官能化的分支烯烃共聚物的热熔粘合剂实现,该分支烯烃共聚物具有:
-10至50kg/mol、优选20至50kg/mol的数均分子量(Mn),根据ISO 16014-4和ASTMD6474方法在150℃下在Agilent 7890型GC箱周围构建的Polymer Char上测量;
-5至65J/g、优选5至30J/g的焓(ΔH),根据ISO 11357-1:2016使用TAInstruments的差示扫描量热计Q100测量;
-2至6、优选严格地大于3且小于6的多分散性指数(PDI),根据方法ISO 16014-4和ASTM D6474方法在150℃下在Agilent 7890型GC箱周围构建的Polymer Char上测量;
-40至120℃的熔化温度(Tm),根据ISO 11357-1:2016使用TA Instruments的差示扫描量热计Q100测量;
-每条聚合物链至少两个或更多个羟基官能团,已由1H NMR表征;并且
其中无规羟基官能化的分支烯烃共聚物至少部分是结晶的,并且具有低于40%、优选低于30%、更优选15%、甚至更优选低于10%且更优选高于1%、更优选高于5%的结晶度(Xc)水平,根据ISO 11357-1:2016使用TA Instruments的差示扫描量热计Q100测量,并且
其中无规羟基官能化的分支烯烃共聚物由以下组成:至少80mol%的由下式(1)表示的组成单元,任选的由下式(2)表示的组成单元,和0.1至1mol%、优选0.1至0.5mol%的由下式(3)表示的组成单元:
其中:
·R1为H或CH3;
·R2选自包含以下的列表:具有0至10个,在R1=H时优选2至6个且更优选6个,且在R1=CH3时优选0、2或4个碳原子的烃基;
·R3为具有2至10、优选2至8、优选4至8、更优选4或6个碳原子的烃基,
且其中羟基官能化烯烃共聚物已经历了与由下式(4)表示的二、三或多异氰酸酯的加成反应:
其中:
·R4为具有1至10个碳原子的烃基;
·n为1至4、优选1至2、更优选1。
因为无规羟基官能化的分支烯烃共聚物具有Tm并且ΔH为5或更大,意味着无规羟基官能化的分支烯烃共聚物不是无定形的且至少部分地为结晶的。
在一些实施方案中,由下式(3)表示的组成单元选自包含以下的组:3-丁烯-1-醇,3-丁烯-2-醇,5-己烯-1-醇,5-己烯-1,2-二醇,7-辛烯-1-醇,7-辛烯-1,2-二醇,5-降冰片烯-2-甲醇,10-十一碳烯-1-醇;优选5-己烯-1-醇。
在一些实施方案中,已使用溶液法进行了聚合。
在一些优选的实施方案中,使用烯烃聚合催化剂体系进行共聚,其提供具有5%至40%、优选10%-30%、更优选10%-25%的结晶度的半结晶无规羟基官能化的分支烯烃共聚物。
在一些实施方案中,已进行了称为脱灰的纯化步骤,该步骤由除去在聚合后残留在树脂中的痕量无机杂质组成。
本发明的另一个方面是根据本发明的基于聚氨酯的热熔粘合剂的用途,用于将金属、玻璃、极性聚合物或金属与玻璃、金属与极性聚合物、玻璃与极性聚合物、金属与聚烯烃、玻璃与聚烯烃、极性聚合物与聚烯烃或聚烯烃与聚烯烃胶合到一起。
具体实施方式
本发明优选涉及基于聚烯烃的热熔粘合剂树脂,其包含与二、三或多异氰酸酯反应形成交联体系的羟基官能团。
除了聚氨酯粘合剂已知的高粘合强度以外,本发明的基于聚烯烃的聚氨酯热熔粘合剂因聚烯烃的高阻水性而预期提供优异的耐久性。使用相对高分子量的无规分支羟基官能化的烯烃共聚物树脂,对应的聚氨酯热熔粘合剂将不仅显示对极性基材诸如金属、玻璃和极性聚合物的良好的粘附,而且对低表面能材料诸如聚烯烃也显示良好的粘附。
为了确保将保证与各种基材强粘合的充分交联的体系,优选无规羟基官能化的分支烯烃共聚物每条聚合物链含有多于两个羟基官能团。在优选的实施方案中,无规羟基官能化的分支烯烃共聚物每条聚合物链含有至少两个或更多个羟基官能团。
根据本发明,基于聚烯烃的热熔粘合剂树脂包含至少一种第一烯烃单体和羟基官能化的C2至C12、优选C4至C12、更优选C4至C10烯烃单体的共聚物,其已经历了与二、三或多异氰酸酯的加成反应,产生了根据式(5)的交联体系:
其中:
·z、z'为0.1至1mol%;
·x、x'为至少80mol%;
·y为0或100-(x+z)mol%,且y'为0或100-(x'+z')mol%;
·R1为H或CH3;
·R2选自包含以下的列表:具有0至10个,在R1=H时优选2至6个且更优选6个,且在R1=CH3时优选0、2或4个碳原子的烃基;
·R3为具有2至10、优选2至8、优选4至8、更优选4或6个碳原子的烃基;
·R4为具有1至10个碳原子的烃基;
·n为1至4、优选1至2、更优选1。
在一些实施方案中,由于环境反应的性质,并非共聚物中存在的所有羟基都已与异氰酸酯官能团反应,优选至少40%、优选多于50%的OH基已反应。
因为并非共聚物中存在的所有羟基都反应,在一些实施方案中,优选每条聚合物链具有多于2个羟基官能团以确保有效交联。
在一些实施方案中,第一烯烃单体为乙烯或丙烯、优选丙烯。
在一些实施方案中,根据本发明的热熔粘合剂树脂是基于聚烯烃的共聚物,优选由第一烯烃单体与任选的选自包含乙烯或C3至C12烯烃单体的列表的第二烯烃单体和选自包含羟基官能化的C2至C12、优选C4至C12烯烃单体的列表的第三官能化烯烃单体的聚合产生的三元共聚物。
在优选的实施方案中,第二烯烃单体是“未官能化、未活化的烯烃单体”,意指仅由碳原子和氢原子组成的烯烃单体。
在一些实施方案中,当第一烯烃单体是乙烯时,优选第二烯烃单体是1-丁烯、1-己烯或1-辛烯。
在一些实施方案中,当第一烯烃单体是丙烯时,优选第二烯烃单体是乙烯、1-丁烯、1-己烯或1-辛烯。
在一些实施方案中,第三单体是羟基官能化烯烃单体,优选3-丁烯-1-醇、3-丁烯-2-醇、5-己烯-1-醇、5-己烯-1,2-二醇、7-辛烯-1-醇、7-辛烯-1,2-二醇、5-降冰片烯-2-甲醇、10-十一碳烯-1-醇,优选5-己烯-1-醇。
在一些实施方案中,使用受保护的羟基官能化的C4至C12、优选C6至C12、优选C6至C10、优选C6至C8烯烃单体在溶液法中制成热熔粘合剂树脂。通常,保护基团是甲硅烷基卤化物、三烷基铝络合物、二烷基铝烷氧化物络合物、二烷基镁络合物、二烷基锌络合物或三烷基硼络合物。
虽然这非必要,但除去在聚合过程后残留在聚合物树脂中的痕量无机杂质诸如铝氢氧化物氧化物物类的纯化步骤是优选的。
这样做获得了最佳的粘附强度。发明人相信通过从树脂中除去无机杂质,允许有更多羟基官能团可用于增强树脂与极性材料的粘合性质。
根据本发明,用根据式(4)的具有异氰酸酯的二、三或多异氰酸酯进行羟基官能化聚烯烃的加成反应:
其中:
·R4为具有1至10个碳原子的烃基;
·n为1至4、优选1至2、更优选1。
在一些实施方案中,异氰酸酯选自包含1,6-二异氰酸己烷(HDI)、4,4'-亚甲基二苯基二异氰酸酯(MDI)、亚甲基双(4-环己基异氰酸酯)(HMDI)的列表。
实施例
下式(6)表示本发明的非限制性实施例,其中所用异氰酸酯是二异氰酸酯。
这些官能化烯烃三元共聚物HMA的可调官能团使得它们非常适合于胶合相同或不同的极性基材诸如金属、玻璃、木材和极性聚合物。
此外,官能化烯烃三元共聚物HMA的一般非极性性质提供了对诸如聚烯烃(即,HDPE、LDPE、LLDPE、PP)的低表面能基材的优异的粘附,使得这些HMA非常适合于胶合聚烯烃与聚烯烃,或胶合聚烯烃与诸如金属、玻璃、木材和极性聚合物的极性基材。
以下实施例并非限制性实施例,并且已利用以下单体来实现:丙烯(C3),1-己烯(C6)和5-己烯-1-醇(C6OH)。然而,可使用其它单体来实现本发明。
聚(C3-共-C6-共-C6OH)的合成
使用装填有五甲基庚烷(PMH)溶剂(1L)的不锈钢反应器(2L)、使用600rpm的搅拌速度进行了聚合实验。在惰性干燥氮气气氛下在手套箱中制备了催化剂和共聚单体溶液。
首先将反应器加热至40℃,之后添加TiBA(在甲苯中的1.0M溶液,2mL)、1-己烯(净10mL)和三乙基铝(TEA)钝化的5-己烯-1-醇(在甲苯中的1.0M溶液,TEA:5-己烯-1-醇(摩尔比)=1,10mL)。在40℃下用气态丙烯(100g)装载反应器,并且将反应器加热至130℃的所需聚合温度,从而产生约15巴的丙烯分压。一旦达到了设定温度,通过注入在MAO(于甲苯中的30重量%溶液,11.2mmol)中的预活化催化剂前体二甲基双((2-氧代-3-(二苯并-1H-吡咯-1-基)-5-(甲基)苯基)-2-苯氧基)-2,4-戊二基铪(IV)[CAS 958665-18-4]、别名[[2',2”'-[(1,3-二甲基-1,3-丙二基)双(氧基-κO)]双[3-(9H-咔唑-9-基)-5-甲基[1,1'-联苯]-2-酚-κO]](2-)]二甲基]铪(Hf-O4,2μmol)来引发聚合反应。通过将聚合物溶液倒入含有脱矿质水/iPrOH(50重量%,1L)和Irganox 1010(1.0M,2mmol)的烧瓶容器中来停止反应。过滤所得悬浮液并且在80℃下在真空烘箱中干燥,之后添加作为抗氧化剂的Irganox 1010。获得了白色粉末聚(丙烯-共-1-己烯-共-5-己烯-1-醇)(25.6g)。
脱灰规程
可纯化由溶液法获得的三元共聚物以除去诸如铝氢氧化物氧化物的痕量无机杂质。为此,将聚(C3-共-C6-共-C6OH)(10g)(表1,项目1)分散于干甲苯(400ml)和浓(37%)HCl(10mL,0.13mol,4.74g)的混合物中,并且在回流下加热直至三元共聚物溶解。一旦聚合物适当地溶解,将甲醇(250ml)加入热混合物中,并且在90-100℃下在搅拌下再加热混合物1小时。然后使聚合物于冷甲醇中沉淀,过滤并用甲醇洗2次。纯化过程的产率为85%。
聚氨酯合成规程
实施例2:聚(C3-共-C6-共-C6O-(MDI)
在110℃下,将脱灰并除气的聚(C3-共-C6-共-C6OH)(0.4mol%OH;Mn=26.6kg·mol-1;PDI=4.6;5.6·10-4mol,15g;表1,项目1)溶解于400ml干甲苯中。该过程在回流和氮气气氛下进行。当获得均匀的混合物时,将新鲜蒸馏的4,4'-亚甲基二苯基二异氰酸酯(1.5·10-3mol,0.375g)(MDI)引入由此获得的聚合物溶液中。10min后,添加作为催化剂的二月桂酸二丁锡(7.9·10-4mol,0.498g)。在110℃下,在氮气气氛下进行反应22h。通过在冷甲醇中沉淀来回收产物并且在60℃下在减压下干燥。反应产率为87%。在干燥后获得的最终产物是部分交联的,并因此难以溶解于例如1,2-二氯苯的常见有机溶剂中。
实施例3:聚(C3-共-C6-共C6O-(HDI)和实施例4:聚(C3-共-C6-共-C6O-(HMDI)
实施例3和实施例4在与用于实施例2的类似条件和规程下合成,区别是分别用1,6-二异氰酸己烷(HDI)和亚甲基双(4-环己基异氰酸酯)(HMDI)替代4,4'-亚甲基二苯基二异氰酸苯酯(MDI)。
表1:根据上述规程生产的具有不同组成的共聚物和三元共聚物的特性
*不溶于1,2-二氯苯中
表2:搭接剪切测试结果
表3:动态机械热分析
图1、2、3和4分别是实施例1、实施例2、实施例3和实施例4的1H NMR谱,其中可观察到官能团水平和共聚单体组成。
测量
尺寸排阻层析(SEC)
SEC测量是根据ISO 16014-4和ASTM D6474方法,在150℃下在Agilent 7890型GC箱周围构建的配备有自动采样器和集成检测器IR4的Polymer Char上进行的。使用1,2-二氯苯(o-DCB)作为洗脱剂,流速为1mL/min。使用计算软件GPC/>处理数据。相对于聚乙烯标准品或聚苯乙烯标准品计算分子量(Mn)(Mw)和PDI。
液态1H NMR
1H NMR和13C NMR波谱是在室温或80℃下使用对于1H和13C分别在400MHz和100.62MHz的拉莫尔频率下运行的Varian Mercury Vx谱仪记录的。对于1H NMR实验,谱宽为6402.0Hz,采集时间1.998s,且记录的扫描数等于64。13C NMR波谱利用24154.6Hz的谱宽、1.3s的采集时间和256次扫描记录。
差示扫描量热法(DSC)
根据ISO 11357-1:2016使用TA Instruments的差示扫描量热计Q100测量熔化(Tm)温度以及转变的熔点的焓(ΔH[J/g])。以10℃/min的加热和冷却速率从-50℃至240℃进行测量。由二次加热和冷却曲线推导转变。
通过比较样品的熔化转变的焓与100%晶态聚丙烯的熔化转变的焓,DSC已被用于测定结晶度(Xc)含量。
动态机械热分析(DMTA)
使用TA Instruments Q800 DMA测量储能模量(E')和损耗模量(E")[MPa]。通过应变受控的温度升高以1Hz的频率测试样品。温度分布是以3℃/min的升高从-150℃至聚合物熔化。玻璃化转变温度计算为tanδ信号的峰。
压缩成型实验
用于搭接剪切试验的膜样品是经由压缩成型,在LabEcon 600高温压机(荷兰Fontijne Presses)上使用PP ISO设置制备的。即将官能化聚烯烃的膜(25mm×12.5mm×0.5mm)以重叠表面12.5mm装载于基材之间:PP-PP,钢-钢,铝-铝或它们的组合。然后,应用压缩成型周期:加热至130℃,不施加力稳定3min,以100kN(0.63MPa)法向力5min,并以10℃/min和100kN(0.63MPa)法向力冷却至40℃。
搭接剪切强度
根据ASTM D1002-10(2019)利用配备有10kN载荷传感器的Zwick Z020型拉伸试验机进行测量。测量前,在室温下调节样品7天。在具有12.5mm重叠表面的试样(10cm×2.5cm)上进行测试。使用140mm的夹头与夹头分离。将样品预加应力至3N,然后用100mm/min恒定十字头速度装载。为了计算搭接剪切强度,报告力值除以试样的粘合表面(25mm×12.5mm)。报告值是每种组合物的至少5次测量的平均值。
Claims (8)
1.基于聚氨酯的热熔粘合剂,其包含无规羟基官能化的分支烯烃共聚物,所述共聚物具有:
·10至50kg/mol、优选20至50kg/mol的数均分子量(Mn),根据ISO 16014-4和ASTMD6474方法在150℃下在Agilent 7890型GC箱周围构建的Polymer Char 上测量;
·5至65J/g、优选5至30J/g的焓(ΔH),根据ISO 11357-1:2016使用TAInstruments的差示扫描量热计Q100测量;
·2至6、优选严格地大于3且小于6的多分散性指数(PDI),根据方法ISO 16014-4和ASTM D6474方法在150℃下在Agilent 7890型GC箱周围构建的Polymer Char 上测量;
·40至120℃的熔化温度(Tm),根据ISO 11357-1:2016使用TA Instruments的差示扫描量热计Q100测量;
·每条聚合物链至少两个或更多个羟基官能团,已由1H NMR表征,并且
其中所述无规羟基官能化的分支烯烃共聚物至少部分是结晶的,并且具有低于40%、优选低于30%、更优选15%、甚至更优选低于10%且更优选高于1%、更优选高于5%的结晶度(Xc)水平,根据ISO 11357-1:2016使用TAInstruments的差示扫描量热计Q100测量,并且
其中所述无规羟基官能化的分支烯烃共聚物由以下组成:
-至少80mol%的由下式(1)表示的组成单元;
-任选的由下式(2)表示的组成单元;和
-0.1至1mol%、优选0.1至0.5mol%的由下式(3)表示的组成单元:
其中:
R1为H或CH3;
R2选自包含以下的列表:具有0至10个,在R1=H时优选2至6个且更优选6个,且在R1=CH3时优选0、2或4个碳原子的烃基;
R3为具有2至10、优选2至8、优选4至8、更优选4或6个碳原子的烃基;
且其中羟基官能化的烯烃共聚物已经历了与由下式(4)表示的二、三或多异氰酸酯的加成反应:
其中:
R4为具有1至10个碳原子的烃基;
n为1至4、优选1至2、更优选1。
2.根据权利要求1所述的基于聚氨酯的热熔粘合剂,其中所述由下式(3)表示的组成单元选自包含以下的组:3-丁烯-1-醇,3-丁烯-2-醇,5-己烯-1-醇,5-己烯-1,2-二醇,7-辛烯-1-醇,7-辛烯-1,2-二醇,5-降冰片烯-2-甲醇,10-十一碳烯-1-醇;优选5-己烯-1-醇。
3.根据前述权利要求中任一项所述的基于聚氨酯的热熔粘合剂,其中已使用溶液法进行聚合。
4.根据权利要求3所述的基于聚氨酯的热熔粘合剂,其中在所述加成反应之前已进行由除去在聚合后残留在树脂中的痕量无机杂质组成的纯化步骤。
5.根据前述权利要求中任一项所述的基于聚氨酯的热熔粘合剂,其包含以下交联体系:
其中:
z、z'为0.1至1mol%,
x、x'为至少80mol%,
y为0或100-(x+z)mol%,且y'为0或100-(x'+z')mol%,
R1为H或CH3,
R2选自包含以下的列表:具有0至10个,在R1=H时优选2至6个且更优选6个,且在R1=CH3时优选0、2或4个碳原子的烃基,
R3为具有2至10、优选2至8、优选4至8、更优选4或6个碳原子的烃基,
R4为具有1至10个碳原子的烃基;
n为1至4、优选1至2、更优选1。
6.根据前述权利要求中任一项所述的基于聚氨酯的热熔粘合剂的用途,用于将金属、玻璃、极性聚合物或金属与玻璃、金属与极性聚合物、玻璃与极性聚合物、金属与聚烯烃、玻璃与聚烯烃或极性聚合物与聚烯烃胶合到一起。
7.根据前述权利要求中任一项所述的基于聚氨酯的热熔粘合剂,其具有根据ASTMD1002-10(2019)利用配备有10kN载荷传感器的Zwick Z020型拉伸试验机测量的以下粘合性质中的至少一者、优选两者、更优选全部:
3MPa以上、优选4MPa以上、更优选5MPa以上、甚至更优选9MPa以上的钢与钢的搭接剪切强度,
3MPa以上、优选4MPa以上、更优选5MPa以上的铝与铝的搭接剪切强度,
3MPa以上、优选4MPa以上、更优选5MPa以上的聚烯烃与聚烯烃的搭接剪切强度。
8.根据前述权利要求中任一项所述的基于聚氨酯的热熔粘合剂,其具有根据本申请的动态机械热分析(DMTA)章节中所述方法测量的在20℃下115MPa以上且在-40℃下2030MPa以上的储能模量(E'),和根据本申请的动态机械热分析(DMTA)章节中所述方法测量的在20℃下17MPa以上且在-40℃下36MPa以上的损耗模量(E")。
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