CN112552492A - 共聚物以及聚氨酯的制备方法 - Google Patents
共聚物以及聚氨酯的制备方法 Download PDFInfo
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- CN112552492A CN112552492A CN202010966892.6A CN202010966892A CN112552492A CN 112552492 A CN112552492 A CN 112552492A CN 202010966892 A CN202010966892 A CN 202010966892A CN 112552492 A CN112552492 A CN 112552492A
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- Prior art keywords
- cyclic ether
- mol
- membered cyclic
- lactone
- producing
- Prior art date
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Abstract
一种共聚物以及聚氨酯的制备方法。提供一种能够容易地控制内酯聚合物的分子量,能够容易且完全地去除作为残留催化剂的废酸,着色或杂质的生成少并且在工业上非常简单且无浪费地制备高质量的聚醚的方法。本发明涉及一种五元环环状醚(A)和内酯类(B)的共聚物的制备方法,其特征在于,在10℃~50℃的温度范围内进行共聚反应,将杂多酸作为催化剂,将含有羟基、氨基、巯基的含有活性氢原子的化合物作为反应引发剂(C)使用,并且并用三元环至四元环环状醚(D)。
Description
技术领域
本发明涉及一种五元环环状醚和内酯类的共聚物的制备方法。
背景技术
以往,已知环状醚类例如四氢呋喃(THF)通过质子酸、路易斯酸、离子络合物等阳离子系催化剂聚合。另外,已知内酯类例如β-丙内酯或ε-己内酯等既通过阳离子催化剂容易聚合,也通过阴离子催化剂容易聚合。这样获得的聚四亚甲基醚二醇或聚己内酯二醇(polycaprolactone glycol)等聚合物作为聚氨酯树脂、聚酯树脂的软链段是有用的材料。
聚四亚甲基醚二醇将聚醚作为主链,而聚己内酯二醇等内酯类的开环聚合物将聚酯作为主链,因此在耐水解性、耐热性、耐光性等方面,各自存在彼此相反的优缺点。作为弥补这些彼此的欠点的解决方案,可考虑通过THF和内酯类的共聚获得的聚醚聚酯二醇。但是,THF和内酯类之间在可聚合性差异很大,并且难以使它们共聚。作为THF和ε-己内酯的共聚方法,已知将路易斯酸作为催化剂的方法(非专利文献1),但是所获得的共聚物嵌段性高,即THF和ε-己内酯不能随机聚合,而是成为聚四氢呋喃和聚ε-己内酯的嵌段共聚物或者聚四亚甲基醚和聚己内酯二醇的混合物之类的化合物。
为了解决这些问题,已有报道THF和ε-己内酯的共聚方法,其特征在于,在催化剂中作为路易斯酸使用三氟化硼(BF3)系、发烟硫酸系、氟硫酸等,并且并用三元环至四元环状醚(例如,专利文献1)。
另外,已有报道使用钛酸四丁酯之类阴离子开环聚合催化剂或者通过在100℃~200℃的高温下进行反应而使内酯和环状醚共聚的方法(例如,专利文献2)。
现有技术文献
专利文献
专利文献1:日本特开昭63-178131号公報
专利文献2:日本特开2019-23256号公報
非专利文献
非专利文献1:“聚合物杂志(Polymer Journal)”,(日本),1971年,第3卷,第3号,第389-393页
发明内容
不能仅通过并用三元环至四元环状醚来控制共聚物的分子量,因此无法获得目标分子量的共聚物。而且,三氟化硼系、发烟硫酸系、氟硫酸等催化剂体系存在在后续处理中需要进行氟化处理或大量废酸处理等的问题。另外,由于基于高温的阴离子聚合同时发生酯交换反应等副反应而还含有大量低聚合物等,因此以往的制备方法存在无法控制共聚物的分子量、大量废酸处理以及高温下聚合因副反应而产生杂质的问题。
鉴于上述实情,本发明人等精心研究的结果发现,在将杂多酸催化剂的使用量减少至微量的条件下,将三元环至四元环环状醚作为引发剂并用而进行聚合的工艺,从而能够使得五元环环状醚和内酯类共聚的制备方法,以此完成了本发明。
即,本发明的共聚物的制备方法如下。
[1]一种共聚物的制备方法,所述共聚物为五元环环状醚(A)和内酯类(B)的共聚物,其中,在10℃~50℃的温度范围内进行共聚反应,将路易斯酸和/或固体酸(优选杂多酸)作为催化剂,将含有羟基、氨基、巯基的含有活性氢原子的化合物作为反应引发剂(C)任选地使用,并且并用三元环至四元环环状醚(D)。
[2]根据[1]所述的共聚物的制备方法,其中,所述五元环环状醚(A)为四氢呋喃类,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述五元环环状醚(A)的添加量(配合比率)为1摩尔%~90摩尔%。
[3]根据[1]所述的共聚物的制备方法,其中,内酯类(B)能够具有取代基,并为β-丙内酯、γ-丁内酯、δ-戊内酯或者ε-己内酯,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,内酯类(B)的添加量(配合比率)为1摩尔%~90摩尔%。
[4]根据[1]所述的共聚物的制备方法,其中,所述反应引发剂(C)为具有一个以上羟基的羟基化合物,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述反应引发剂(C)的添加量为0摩尔%~20摩尔%。
[5]根据[1]所述的共聚物的制备方法,其中,所述三元环至四元环环状醚(D)为环氧化物类或者氧杂环丁烷类,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述三元环至四元环环状醚(D)的添加量为0.1摩尔%~50摩尔%。
[6]根据[1]所述的共聚物的制备方法,其中,所述催化剂为未处理的杂多酸,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述催化剂的添加量为0.01摩尔%~2摩尔%。
[7]根据[1]所述的共聚物的制备方法,其中,所述共聚物的制备方法为五元环环状醚(A)和内酯类(B)的共聚物的制备方法,在10℃~50℃的温度范围内进行共聚反应,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,将0.01摩尔%~2摩尔%的杂多酸作为催化剂,将0摩尔%~5摩尔%的具有一个以上羟基的羟基化合物作为反应引发剂(C),并且并用40摩尔%~80摩尔%的四氢呋喃类的五元环环状醚(A)、20摩尔%~60摩尔%的ε-己内酯的内酯类(B)以及5摩尔%~20摩尔%的三元环至四元环环状醚(D)。
[8]一种聚氨酯的制备方法,其中,使得通过[1]至[7]中任一项所述的制备方法获得的共聚物和多异氰酸酯化合物进行反应来制备聚氨酯。
本发明的五元环环状醚和内酯类的共聚物的制备方法在未处理杂多酸且以微量使用的情况下,能够通过离子交换树脂简单地吸附并去除杂多酸,之后,仅通过蒸馏掉未反应的环状醚即可获得五元环环状醚和内酯类的共聚物。本发明的五元环环状醚和内酯类的共聚物的制备方法不需要水解操作或清洗操作等的工序,因此其为也不需要处理产生的废酸或废水的极其简单的制备方法。
另外,本发明的五元环环状醚和内酯类的共聚物的制备方法根据引发剂的种类、使用量、目标聚合物的质量、分子量等决定最佳聚合反应温度,因此聚合反应在惰性有机溶剂下也可以实施。而且,在50℃以下的温度下获得的共聚物不存在副反应引起的质量劣化,例如着色。
另外,本发明的五元环环状醚和内酯类的共聚物的制备方法可以通过改变催化剂的使用量以及引发剂的添加量来容易地控制分子量,因此能够实现共聚物的分子量的控制。
因而,本发明的五元环环状醚和内酯类的共聚物的制备方法是在工业上非常简单且无浪费并能够获得高质量的聚醚的优异的方法。
具体实施方式
下面,参考优选实施方式更加详细地说明本发明。
作为具体的内酯类(B)的例,包括β-丙内酯、β-丁内酯、β-戊内酯、γ-丁内酯、γ-戊内酯、γ-辛内酯、δ-戊内酯、β-甲基-δ-戊内酯、δ-硬脂酸内酯(δ-stearolactone)、ε-己内酯、2-甲基-ε-己内酯、4-甲基-ε-己内酯、ε-辛内酯、ε-棕榈内酯等。
作为3~4元环环状醚(D),可以例举环氧乙烷、环氧丙烷、环氧氯丙烷等环氧化物类、3-甲基氧杂环丁烷、3,3-二(氯甲基)-氧杂环丁烷等氧杂环丁烷类。
当使用3~4元环环状醚(D)时,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,其添加量优选为0.1摩尔%~50摩尔%,特别优选为0.1摩尔%~10摩尔%。当不使用3~4元环环状醚(D)时,不进行共聚且成为环状醚聚合物和内酯类聚合物的混合物之类的化合物。当3~4元环环状醚(D)大于50摩尔%时,聚合物的组合比率发生大的变化,因此导致物性降低,并且,产生大量的未反应物,因此去除其需要成本,从而不优选。
作为五元环环状醚(A),可以例举四氢呋喃、2-甲基四氢呋喃、3-甲基四氢呋喃等四氢呋喃类、二氧戊环。
五元环环状醚(A)和内酯类(B)的共聚方法的制备方法的特征在于,当使用五元环状醚(A)时,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,其添加量优选为1摩尔%~90摩尔%,特别优选为10摩尔%~80摩尔%。
含有活性氢原子的化合物是指含有羟基、氨基、巯基的化合物,且作为反应引发剂(C)使用。作为含有羟基的化合物的例,包括甲醇、乙醇、丙醇、正丁醇、第二丁醇、第三丁醇、烯丙醇、甲基丙烯酸2-羟乙酯等脂肪族醇、苯甲醇或苯甲基甲醇(phenylmethyl carbinol)之类芳族醇、环己醇或三甲基己醇之类脂环式醇、乙二醇、丙二醇、1,4-丁二醇、聚乙二醇、聚丙二醇、聚亚氧四甲基二醇(polyoxytetramethylene glycol)、甘油、三羟甲基丙烷、环己二醇、二甲苯二醇(xylylene glycol)等多元醇类,作为其它各种酚类、有机羧酸类、含有氨基的化合物的例,包括甲基-、乙基-、正丙基-、异丙基-、正丁基-、仲丁基、叔丁基之类脂肪族伯胺以及与其对应的二烷基胺之类脂肪族仲胺、苯胺、甲苯胺(toluidine)、二苯胺、环己胺、哌啶之类芳香族、脂环族以及杂环胺、乙二胺、丙二胺、己二胺、邻、间或对苯二胺、1,4-环己二胺、哌嗪、二亚乙基三胺、4,4’,4”-亚甲基三苯胺(4,4’,4”-methylidynetrianiline)等脂肪族、芳香族、脂环族以及杂环多胺。作为含有巯基的化合物的例,包括甲基-、乙基-、丙基-、丁基-之类脂肪族硫醇、苄硫醇之类芳香族硫醇、二硫代乙二醇(ethylene dithioglycol)、二甲苯二硫醇(xylylene dimercaptan)、巯基乙醇等。
五元环环状醚(A)和内酯类(B)的共聚方法的制备方法的特征在于,当作为引发剂(C)使用多元醇时,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,其使用量优选为0摩尔%~20摩尔%(优选排除0摩尔%),特别优选为0.1摩尔%~1.0摩尔%。当引发剂(C)的使用量大于20摩尔%时,产物的分子量小且不产生足够的高分子体。当未使用引发剂(C)时,无法控制分子量且无法获得目标分子量的化合物。
作为在本发明中使用的固体酸,可以例举二氧化硅、二氧化钛、二氧化锆、氧化铝、杂多酸(例如,磷钨酸、硅钨酸、磷钼酸、硅钼酸)等。作为路易斯酸,可以例举三氟化硼、五氟化磷、五氟化锑、五氯化锑、氯化铝、四氯化钛、四氯化锡等金属或非金属卤化物。进而,作为使用它们的催化剂时的形式,可以例举三氟化硼、五氯化锑等和***、四氢呋喃等链状以及与环状醚的络合物等。
五元环环状醚(A)和内酯类(B)的共聚方法的制备方法的特征在于,在本发明中使用的路易斯酸和/或固体酸催化剂的使用量为相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,优选为2摩尔%以下,特别优选为0.1摩尔%~1.0摩尔%。特征在于,催化剂的使用量极少,因此对其的去除也容易。当催化剂的使用量大于2摩尔%时,发热会显著,并且分子量分布极大地变宽,不仅如此,副反应引起质量劣化,例如着色显著。另外,难以用离子交换树脂去除催化剂,因此需要水清洗工序,催化剂的去除需要成本,从而不优选。
在实施本发明的方面,聚合反应温度优选为50℃以下,特别优选为0℃~40℃,但是最佳温度取决于引发剂(C)的种类、使用量、目标聚合物的质量、分子量等,通常为20℃~40℃。聚合反应在惰性有机溶剂中也可以实施。在较低温度下的本体聚合中,进行聚合的同时容易发生结晶,因此优选在苯、甲苯、二甲苯之类惰性有机溶剂中实施。在高于100℃的温度下,分子量分布极大地变宽,不仅如此,副反应引起质量劣化,例如着色显著。另一方面,聚合反应时间与反应速度有关,根据温度、引发剂(C)的种类、使用量等会变化。通常,将其设为2小时~10小时以上。在该聚合体系中,为了简化聚合物的提纯操作且提高质量,优选将聚合进行至未反应的内酯消失为止,需要进行充分的熟化。
使用在本发明中获得的五元环环状醚(A)和内酯类(B)的共聚物的聚氨酯树脂的制备方法没有特别限制,可以用公知的方法等来制备。例如,既可以将多异氰酸酯成分一并加入到多元醇、扩链剂、有机金属催化剂中进行反应,也可以在使多元醇和多异氰酸酯成分进行反应而获得异氰酸酯基末端的预聚物之后,添加扩链剂来进行延伸反应。
作为多异氰酸酯化合物,可以例举具有两个以上异氰酸酯基的芳香族系、脂环族系、脂肪族系等多异氰酸酯等。
作为具体例,可以例举甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、聚亚甲基多苯基多异氰酸酯(MDI)、亚二甲苯基二异氰酸酯(XDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HMDI)等多异氰酸酯等。在此,从易于获得并控制与羟基的反应等方面考虑,优选MDI。
作为扩链剂,可以例举1,3-丙二醇、1,4-丁二醇、1,5-戊二醇等低分子量二元醇。
作为有机金属催化剂,没有特别限制,具体可以例举二丁基氧化锡、二乙酸二丁基锡、二月桂酸二丁基锡、二丁基二氯化锡、二月桂酸二辛基锡等有机锡催化剂、辛酸镍、环烷酸镍、辛酸钴、环烷酸钴、辛酸铋、环烷酸铋等。其中,优选的化合物是有机锡催化剂,更加优选的是二月桂酸二丁基锡。
当五元环环状醚(A)和内酯类(B)的共聚物为100.0重量份时,所述有机金属催化剂的使用量通常在0.0001重量份~5.0重量份的范围内,更加优选为在0.001重量份~3.0重量份的范围内。
以下,说明在本发明中使用的测定方法。
[五元环环状醚和内酯共聚物的数均分子量(Mn)的测定方法]
本发明的内酯聚合物的数均分子量(Mn)例如可以在以下条件下使用凝胶渗透色谱(以下,简称为GPC)来测定。
装置:TOSOH HPLC-8320gPC(日本东曹株式会社制)
色谱柱:TSK gelG4000H+G2500H(同上)
检测器:RI
洗脱液:四氢呋喃
标准物质:聚四亚甲基醚二醇
注入量:100μL
流速:1.0mL/分钟
测定温:40℃
[五元环环状醚和内酯共聚物的色数的测定方法]
本发明的色数可以通过JIS K4101-1993-13方法来求出。
[实施例]
以下,根据实施例说明本发明,但是本发明不限于以下实施例。
[实施例1]
[THF-聚己内酯共聚物的合成]
向500mL四颈可拆分烧瓶中添加ε-己内酯(B)63.3g(0.56摩尔,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数为50摩尔%,东京化成工业株式会社制)、THF(A)40.0g(0.56摩尔,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数为50摩尔%)、1,4-丁二醇(C)1.7g(0.02摩尔,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数为1.6摩尔%,日本岸田化学株式会社制)、磷钨酸(催化剂)0.6g(0.0003摩尔,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数为0.02摩尔%,日本新金属株式会社制),并安装温度计、氮气密封件、搅拌装置。在25℃下搅拌15分钟后,向其中添加环氧丙烷(D)6.4g(0.11摩尔,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数为10.0摩尔%,日本岸田化学株式会社制),并在25℃下搅拌4小时。接着,向该反应混合物中作为清洗溶剂加入THF100mL以及离子交换树脂IRA-96S50g(日本Organo株式会社制)并搅拌2小时。过滤该反应混合物,通过减压蒸馏从滤液中去除THF,获得聚合物。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[实施例2]
[THF-聚己内酯共聚物的合成]
除了将实施例1的ε-己内酯改变成37.7g(0.33摩尔),THF改变成55.5g(0.77摩尔)之外,通过与实施例1相同条件、相同操作来进行聚合反应。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[实施例3]
[3-甲基-THF-聚己内酯共聚物的合成]
除了将实施例1的THF40.0g(0.56摩尔)替换成3-甲基-THF48.2g(0.56摩尔)之外,通过与实施例1相同条件、相同操作来进行聚合反应。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[实施例4]
[二氧戊环-聚己内酯共聚物的合成]
除了将实施例1的THF40.0g(0.56摩尔)替换成1,3-二氧戊环41.5g(0.56摩尔,日本岸田化学株式会社制)之外,通过与实施例1相同条件、相同操作来进行聚合反应。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[实施例5]
[THF-聚己内酯共聚物的合成]
除了将实施例1的磷钨酸0.6g(0.0003摩尔)替换成三氟化硼四氢呋喃络合物1.5g(0.01摩尔,Sigma Aldrich日本制)之外,通过与实施例1相同条件、相同操作来进行聚合反应。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[实施例6]
[THF-聚己内酯共聚物的合成]
除了将实施例1的1,4-丁二醇1.7g(0.02摩尔)改变成2.4g(0.03摩尔)之外,通过与实施例1相同条件、相同操作来进行聚合反应。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[实施例7]
[THF-聚己内酯共聚物的合成]
除了将实施例1的1,4-丁二醇1.7g(0.02摩尔)改变成3.2g(0.04摩尔)之外,通过与实施例1相同条件、相同操作来进行聚合反应。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[实施例8]
<THF-聚己内酯共聚物的合成>
除了未使用实施例1的1,4-丁二醇1.7g(0.02摩尔)之外,通过与实施例1相同条件、相同操作来进行聚合反应。THF的种类、各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[比较例1]
<THF-聚己内酯共聚物的合成>
除了将实施例1的反应温度设为60℃之外,通过与实施例1相同条件、相同操作来进行聚合反应。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
[比较例2]
<THF-聚己内酯共聚物的合成>
除了将实施例1的催化剂添加量设为2.1摩尔%之外,通过与实施例1相同条件、相同操作来进行聚合反应。向所获得的反应混合物中作为清洗溶剂加入了THF100mL以及离子交换树脂IRA-96S50g(日本Organo株式会社制)并搅拌2小时,并过滤该反应混合物。滤液浑浊且pH为酸性,明显表明残留有催化剂。因此,向滤液中添加离子交换水100g,在60℃下搅拌1小时之后,静止1小时,分出水层并废弃。该操作重复三次。对所获得的油层,加入离子交换树脂IRA-96S50g(日本Organo株式会社制)并搅拌2小时。过滤该反应混合物。通过减压蒸馏从滤液中去除THF,获得聚合物。各原料的组合比、反应温度/搅拌时间以及所获得的聚合物的收率、数均分子量(Mn)、色数的分析结果示于表1中。
表1
如下说明在表1中记载的缩写。
CL:ε-己内酯
3Me THF:3-甲基-四氢呋喃
DOX:1,3-二氧戊环
PO:环氧丙烷
[产业可利用性]
如从实施例以及比较例显然可知那样,通过本发明的制备方法获得的聚合物通过改变引发剂(C)的添加量能够容易地控制分子量。另外,即使在以微量添加催化剂即杂多酸、金属或非金属卤化物(相对于五元环环状醚(A)和内酯类(B)的合计摩尔数为1摩尔%以下)的情况下,也能够顺利进行共聚反应,而且,若相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,添加2摩尔%以下,则可通过离子交换树脂容易且完全地去除残留催化剂即废酸,之后,仅通过蒸馏掉未反应的THF类即可获得共聚物。另外,反应在常温下进行,因此能够获得着色或杂质生成少且具有令人满意的色数的共聚物。本发明的制备方法是在工业上非常简单且无浪费并能够获得高质量的聚醚的优异的制备方法。
Claims (8)
1.一种共聚物的制备方法,所述共聚物为五元环环状醚(A)和内酯类(B)的共聚物,其中,
在10℃~50℃的温度范围内进行共聚反应,将杂多酸作为催化剂,将含有羟基、氨基、巯基的含有活性氢原子的化合物作为反应引发剂(C)使用,并且并用三元环至四元环环状醚(D)。
2.根据权利要求1所述的共聚物的制备方法,其中,
所述五元环环状醚(A)为四氢呋喃类,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述五元环环状醚(A)的添加量为1摩尔%~90摩尔%。
3.根据权利要求1所述的共聚物的制备方法,其中,
内酯类(B)能够具有取代基,并为β-丙内酯、γ-丁内酯、δ-戊内酯或者ε-己内酯,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,内酯类(B)的添加量为1摩尔%~90摩尔%。
4.根据权利要求1所述的共聚物的制备方法,其中,
所述反应引发剂(C)为具有一个以上羟基的羟基化合物,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述反应引发剂(C)的添加量为0摩尔%~20摩尔%。
5.根据权利要求1所述的共聚物的制备方法,其中,
所述三元环至四元环环状醚(D)为环氧化物类、氧杂环丁烷类,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述三元环至四元环环状醚(D)的添加量为0.1摩尔%~50摩尔%。
6.根据权利要求1所述的共聚物的制备方法,其中,
所述催化剂为未处理的杂多酸,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,所述催化剂的添加量为0.01摩尔%~2摩尔%。
7.根据权利要求1所述的共聚物的制备方法,其中,
所述共聚物的制备方法为五元环环状醚(A)和内酯类(B)的共聚物的制备方法,在10℃~50℃的温度范围内进行共聚反应,相对于五元环环状醚(A)和内酯类(B)的合计摩尔数,将0.01摩尔%~2摩尔%的杂多酸作为催化剂,将0摩尔%~5摩尔%的具有一个以上羟基的羟基化合物作为反应引发剂(C),并且并用40摩尔%~80摩尔%的四氢呋喃类的五元环环状醚(A)、20摩尔%~60摩尔%的ε-己内酯的内酯类(B)以及5摩尔%~20摩尔%的三元环至四元环环状醚(D)。
8.一种聚氨酯的制备方法,其中,
使得通过权利要求1至7中任一项所述的制备方法获得的共聚物和多异氰酸酯化合物进行反应来制备聚氨酯。
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JPS63178131A (ja) * | 1987-01-19 | 1988-07-22 | Hodogaya Chem Co Ltd | テトラヒドロフランとε―カプロラクトンの共重合方法 |
JPH09291144A (ja) * | 1995-08-31 | 1997-11-11 | Hodogaya Chem Co Ltd | ポリエーテルの製造方法 |
CN101243119A (zh) * | 2005-08-17 | 2008-08-13 | 旭硝子株式会社 | 聚酯醚多(一)元醇的制造方法 |
CN109749065A (zh) * | 2019-01-07 | 2019-05-14 | 青岛科技大学 | 一种二元催化剂催化的大环内酯共聚物高效制备方法 |
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JP6971074B2 (ja) | 2017-07-24 | 2021-11-24 | 株式会社ダイセル | オキセタン環含有ラクトン重合体、及びその製造方法 |
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- 2020-08-20 JP JP2020139410A patent/JP2021055048A/ja active Pending
- 2020-08-26 TW TW109129159A patent/TW202112893A/zh unknown
- 2020-09-15 CN CN202010966892.6A patent/CN112552492A/zh active Pending
- 2020-09-18 KR KR1020200120736A patent/KR20210036821A/ko unknown
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JPS63178131A (ja) * | 1987-01-19 | 1988-07-22 | Hodogaya Chem Co Ltd | テトラヒドロフランとε―カプロラクトンの共重合方法 |
JPH09291144A (ja) * | 1995-08-31 | 1997-11-11 | Hodogaya Chem Co Ltd | ポリエーテルの製造方法 |
CN101243119A (zh) * | 2005-08-17 | 2008-08-13 | 旭硝子株式会社 | 聚酯醚多(一)元醇的制造方法 |
CN109749065A (zh) * | 2019-01-07 | 2019-05-14 | 青岛科技大学 | 一种二元催化剂催化的大环内酯共聚物高效制备方法 |
Cited By (2)
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CN114133537A (zh) * | 2021-12-10 | 2022-03-04 | 开滦(集团)有限责任公司 | 一种聚甲醛-聚己内酯共聚物及其制备方法 |
CN114133537B (zh) * | 2021-12-10 | 2023-09-12 | 开滦(集团)有限责任公司 | 一种聚甲醛-聚己内酯共聚物及其制备方法 |
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KR20210036821A (ko) | 2021-04-05 |
JP2021055048A (ja) | 2021-04-08 |
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