CN112029086A - 可用于海绵的自催化软泡聚醚多元醇的制备方法 - Google Patents
可用于海绵的自催化软泡聚醚多元醇的制备方法 Download PDFInfo
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
本发明属于聚醚多元醇合成技术领域，具体涉及一种可用于海绵的自催化软泡聚醚多元醇的制备方法。采用多元醇类化合物、端氨基聚醚或叔胺基有机胺中的一种或几种为起始剂，以碱金属或有机胺为催化剂，与环氧烷烃分两个阶段聚合反应，经过精制，得到自催化软泡聚醚多元醇。本发明制备工艺简单，制备的聚醚多元醇官能度为2‑8，分子量能够达到1000‑20000，且聚醚中含有氨基，具有一定的催化活性，可有效降低应用中催化剂的使用量，进而降低制品的VOC含量。另外本发明制备的聚醚多元醇与传统应用于软泡海绵制品的聚醚多元醇相比，可提供更好力学性能。
Description
技术领域
本发明属于聚醚多元醇合成技术领域，具体涉及一种可用于海绵的自催化软泡聚醚多元醇的制备方法。
背景技术
近年来，聚氨酯材料因其具有的诸多优良性能，在我国得到了快速发展。其中占聚氨酯产量很大一部分的软质泡沫塑料因质轻柔软、绝缘、透气、回弹性好、压缩变形小、耐湿、耐老化性能优良，而且耐油、耐有机溶剂、隔音、保温等多种优良特性，用途极其广泛，已被广泛用于各个领域。而传统的聚氨酯软质泡沫塑料在加工过程中会加入一定量的胺类催化剂，胺类催化剂通常具有强烈的气味，并且许多胺类催化剂由于其低分子量而具有高度挥发性。在泡沫加工过程中胺类的释放可能存在安全性和毒性问题，并且在客户操作过程中残留胺的释放是不期望的。
发明内容
针对现有技术的不足，本发明的目的是提供一种可用于海绵的自催化软泡聚醚多元醇的制备方法，制备工艺简单，制备的聚醚多元醇具有一定的催化活性和阻燃性，能够有效降低应用中催化剂的使用量，进而降低制品的VOC含量，用于软泡海绵制品，能够提供更好力学性能。
本发明所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，采用多元醇类化合物、端氨基聚醚或叔胺基有机胺中的一种或几种为起始剂，以碱金属或有机胺为催化剂，与环氧烷烃分两个阶段聚合反应，经过精制，得到自催化软泡聚醚多元醇。
所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，包括以下步骤：
(1)前段聚合反应：首先在反应釜中加入起始剂、催化剂搅拌均匀后，进行氮气置换，测釜内氧含量小于10-300ppm后，抽真空至-0.1～-0.06MPa，升温至90-120℃脱水2-10h，使得水分≦0.1％；开始加入环氧烷烃，保持釜内温度100-120℃，压力0-0.4MPa，进料结束后，内压反应2-6小时，真空脱除未反应完全的环氧烷烃，降温，得中间体聚醚多元醇；
(2)后段聚合反应：将中间体聚醚多元醇、催化剂加入到反应釜中，进行氮气置换，测釜内氧含量小于10-300ppm后，抽真空至-0.1～-0.06MPa，升温至90-120℃脱水2-10h；开始加入环氧烷烃，保持釜内温度100-120℃，压力0-0.4MPa，进料结束后，内压反应2-4小时；抽真空至-0.1～-0.095MPa，110℃氮气鼓泡1h，脱除未反应完全的环氧烷烃单体；聚合完毕，得粗聚醚，加入纯水和吸附剂处理，并在真空下脱水，脱水完毕后对其过滤，得到自催化软泡聚醚多元醇。
其中：
所述的中间体聚醚多元醇的分子量为400-2000，通过控制环氧烷烃的用量控制其分子量在该范围内。
所述的自催化软泡聚醚多元醇官能度为2-8，优选3-4；分子量为1000-10000，优选2000-5000，更优选3000-4000。
所述的多元醇类化合物为甘油、丙二醇、二乙二醇、乙二醇、山梨醇、蔗糖醇、季戊四醇、木糖醇、甘露醇、蔗糖或葡萄糖甙化合物中的一种或几种，优选甘油和/或季戊四醇，其用量占前段聚合反应体系总量的4-10％。
所述的端氨基聚醚是一类具有柔软的聚醚骨架，末端以氨基或胺基(一般为含有活泼氢的仲胺基、伯胺基或多胺基基团)封端的化合物，结构变化包括聚氧乙烯二胺、聚氧丙烯二胺、聚氧乙烯/聚氧丙烯二胺、聚氧丙烯三胺等变化。优选端胺基聚醚其特征为：官能度为2-8，数均分子量为200-5000，总胺：2-20。其用量占前段聚合反应体系总量的10-15％。
所述的叔胺基有机胺为脂肪胺类、醇胺类、酰胺类、脂环胺类、芳香胺类、萘系胺类含活泼氢基团的叔胺基有机胺中的一种或几种。优选二甲基哌嗪、N，N'-二甲基乙二胺。其用量占前段聚合反应体系总量的5-11％。
所述的环氧烷烃为环氧乙烷(EO)、环氧丙烷(PO)或环氧丁烷(BO)中的一种或几种。优选环氧丙烷(PO)和/或环氧丁烷(BO)、环氧丁烷(BO)和/或环氧乙烷(EO)。
优选地，前段聚合反应中采用的环氧烷烃为环氧丙烷(PO)、环氧丁烷(BO)中的一种或两种的组合，两种组合的话，PO：BO比例为5:1-1:5，优选比例为1:1，其用量占前段聚合反应的75-85％。后段聚合反应中采用的环氧烷烃为环氧烷烃为(EO)、环氧丙烷(PO)或环氧丁烷(BO)中的一种或几种，其用量占后段聚合反应的70-80％，EO占后段聚合反应环氧烷烃总量的5-10％，BO与PO可任意比例。
所述的催化剂为氢氧化钠、氢氧化钾、氢氧化铯、二甲胺、三甲胺、吡啶或环己胺中的一种或几种，优选氢氧化钾。步骤(1)中，所述的催化剂的用量为起始剂、催化剂和环氧烷烃总量的0.05-0.5％，优选为0.1-0.25％；步骤(2)中，所述的催化剂的用量为中间体聚醚多元醇、催化剂和环氧烷烃总量的0.05-0.5％，优选为0.1-0.25％。
所述的吸附剂为硅酸镁、硅酸铝或硅酸镁铝中的一种或几种，用量为粗聚醚质量的0.5-2％，优选1-1.5％。
后段聚合反应中，加入纯水和吸附剂处理，纯水的用量为粗聚醚质量的1-4％，优选2-3％。
优选地，步骤(1)为：前段聚合反应：首先在反应釜中加入起始剂、催化剂搅拌均匀后，进行氮气置换，测釜内氧含量小于50-150ppm后，抽真空至-0.095～-0.085MPa，升温至100-110℃脱水5-7h，使得水分≦0.05％；开始加入环氧烷烃，保持釜内温度105-115℃，压力0-0.4MPa，进料结束后，内压反应2-6小时，真空脱除未反应完全的环氧烷烃，降温，得中间体聚醚多元醇；
优选地，步骤(2)为：后段聚合反应：将中间体聚醚多元醇、催化剂加入到反应釜中，进行氮气置换，测釜内氧含量小于50-150ppm后，抽真空至-0.095～-0.085MPa，升温至90-120℃脱水2-10h；开始加入环氧烷烃，保持釜内温度105-115℃，压力0-0.4MPa，进料结束后，内压反应2-4小时；抽真空至-0.1～-0.095MPa，110℃氮气鼓泡1h，脱除未反应完全的环氧烷烃单体；聚合完毕，得粗聚醚，加入纯水和吸附剂处理，并在真空下脱水，脱水完毕后对其过滤，得到自催化软泡聚醚多元醇。
所述的后段聚合反应中，通过控制环氧烷烃的用量，将所得聚醚多元醇分子量控制在1000-10000，粘度250-5000/25℃，水分控制在W0.01-0.1％，pH控制在8.0-11.0，K+：1-10ppm。
与现有技术相比，本发明的有益效果如下：
本发明制备的聚醚多元醇官能度为2-8，分子量能够达到1000-20000，且聚醚中含有氨基，具有一定的催化活性，可有效降低应用中催化剂的使用量，进而降低制品的VOC含量。另外本发明制备的聚醚多元醇与传统应用于软泡海绵制品的聚醚多元醇相比，可提供更好力学性能。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。
实施例1
中间体聚醚多元醇a
在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L高压釜内，加入234.3g端氨基聚醚(f：4，Mn：约230，总胺：8.10-8.70)、93.7g甘油、4gKOH，进行氮气置换，测釜内氧含量小于100ppm后，抽真空至-0.1～-0.095MPa，升温至102.5±2.5℃脱水4小时，使得水分≦0.05％；持续加入环氧丙烷(PO)1672g，控制反应温度107.5±2.5℃，压力0.25MPa，加入完毕后，内压反应3小时(至压力无明显变化)，真空脱除未反应完全的环氧丙烷单体，降温，得中间体聚醚多元醇a，羟值为205mgKOH/g，KOH：0.18％，待用。
室温下在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L反应釜内加入400g中间体聚醚多元醇a、KOH 2.36g，在-0.10～-0.09MPa下真空脱水2h，然后连续进料环氧丙烷(PO)和环氧乙烷(EO)混合物(PO/EO＝92/8)1177g，维持釜内压力0.2MPa，反应温度107.5±2.5℃，加入完毕后，内压反应5.5小时(至压力无明显变化)；脱除未反应完全的环氧乙烷/环氧丙烷单体；对聚合完毕的产物加入纯水32g及吸附剂(硅酸镁)23.7g，搅拌反应4小时充分吸附；在120℃条件下真空脱水4小时，过滤，得到聚醚多元醇A。
分析指标如下：羟值55.9mgKOH/g，f：3.3-3.6，粘度718mPa·s/25℃，pH值9.20，K+：5ppm，水分：0.025％。
实施例2
中间体聚醚多元醇b
在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L高压釜内，加入261.4g端氨基聚醚(f：6，Mn：约440，总胺：6.10-6.80)、203.6g二甲基哌嗪、4gKOH，进行氮气置换，测釜内氧含量小于100ppm后，抽真空至-0.1～-0.095MPa，升温至102.5±2.5℃脱水3h，使得水分≦0.05％；持续加入环氧丁烷(BO)1535g，控制反应温度107.5±2.5℃，压力0.1MPa，加入完毕后，内压反应2小时(至压力无明显变化)，真空脱除未反应完全的环氧丁烷单体，降温，得中间体聚醚多元醇b，羟值为211.7mgKOH/g，KOH：0.19％，待用。
室温下在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L反应釜内加入400g中间体聚醚多元醇b、KOH 2.49g，在-0.10～-0.09MPa下真空脱水2h，然后连续进料环氧丁烷(BO)和环氧乙烷(EO)混合物(BO/EO＝90/10)1229g，维持釜内压力0.2MPa，反应温度107.5±2.5℃，加入完毕后，内压反应4小时(至压力无明显变化)；脱除未反应完全的环氧乙烷/环氧丁烷单体；对聚合完毕的产物加入纯水33g及吸附剂(硅酸镁铝)24.4g，搅拌反应4小时充分吸附；在120℃条件下真空脱水4小时，过滤，得到聚醚多元醇B。
分析指标如下：羟值57.3mgKOH/g，f：3.0-3.1，粘度750mPa·s/25℃，pH值10.01，K+：1ppm，水分：0.017％。
实施例3
中间体聚醚多元醇c
在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L高压釜内，加入161.7g季戊四醇、135.7g二甲基哌嗪、4gKOH，进行氮气置换，测釜内氧含量小于100ppm后，抽真空至-0.1～-0.095MPa，升温至102.5±2.5℃脱水5h，使得水分≦0.05％；持续加入环氧丙烷(PO)和环氧丁烷(BO)混合物(PO/BO＝1/1)1703g，控制反应温度107.5±2.5℃，压力0.3MPa，加入完毕后，内压反应4小时(至压力无明显变化)，真空脱除未反应完全的环氧丙烷/环氧丁烷单体，降温，得中间体聚醚多元醇c，羟值为204.3mgKOH/g，KOH：0.19％，待用。
室温下在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L反应釜内加入400g中间体聚醚多元醇c、KOH 2.49g，在-0.10～-0.09MPa下真空脱水2h，然后连续进料环氧丙烷(PO)、环氧丁烷(BO)和环氧乙烷(EO)混合物(PO/BO/EO＝46/46/8)1203g，维持釜内压力0.1MPa，反应温度107.5±2.5℃，加入完毕后，内压反应6小时(至压力无明显变化)；脱除未反应完全的环氧乙烷/环氧丙烷/环氧丁烷单体；对聚合完毕的产物加入纯水32g及吸附剂(硅酸铝)24g，搅拌反应4小时充分吸附；在120℃条件下真空脱水4小时，过滤，得到聚醚多元醇C。
分析指标如下：羟值56.7mgKOH/g，f：3.0-3.1，粘度720mPa·s/25℃，pH值9.73，K+：1ppm，水分：0.022％。
实施例4
中间体聚醚多元醇d
在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L高压釜内加入104.6gN，N'-二甲基乙二胺、273.3g端氨基聚醚(f：4，Mn：约230，总胺：8.10-8.70)、4gKOH，进行氮气置换，测釜内氧含量小于100ppm后，抽真空至-0.1～-0.095MPa，升温至102.5±2.5℃脱水4h，使得水分≦0.05％；持续加入环氧丙烷(PO)和环氧丁烷(BO)混合物(PO/BO＝1/1)1623g，控制反应温度107.5±2.5℃，压力0.4MPa，加入完毕后，内压反应4小时(至压力无明显变化)，真空脱除未反应完全的环氧丙烷/环氧丁烷单体，降温，得中间体聚醚多元醇d，羟值为200.3mgKOH/g，KOH：0.2％，待用。
室温下在装配有搅拌器、计量器、加热温控装置、冷却装置和压力传感器的3L反应釜内加入400g中间体聚醚多元醇d、KOH 2.49g，在-0.10～-0.09MPa下真空脱水2h，然后连续进料环氧丙烷(PO)、环氧丁烷(BO)和环氧乙烷(EO)混合物(PO/BO/EO＝45/45/10)1171g，维持釜内压力0.3MPa，反应温度107.5±2.5℃，加入完毕后，内压反应7小时(至压力无明显变化)；脱除未反应完全的环氧乙烷/环氧丙烷/环氧丁烷单体；对聚合完毕的产物加入纯水32g及吸附剂(硅酸镁和硅酸铝，二者质量比1：1)23.6g，搅拌反应4小时充分吸附；在120℃条件下真空脱水4小时，过滤，得到聚醚多元醇D。
分析指标如下：羟值56.0mgKOH/g，f：3.0-3.1，粘度690mPa·s/25℃，pH值9.83，K+：4ppm，水分：0.036％。
将实施例1、2、3、4和市售软泡聚醚560D用于软泡泡沫，配方如下：
软泡材料包括A组分和B组分，A组分为聚醚多元醇、扩链剂、催化剂、匀泡剂、发泡剂的混合物，其组成成分的质量比为：聚醚多元醇：硅油：催化剂：匀泡剂：发泡剂＝200：(0.1-0.5)：(0.2-1)：(1-2)：(2-10)；B组分是由异氰酸酯组成；A、B加入量以质量计为：A：B＝100：30-60。
催化剂用量、扩链剂用量、吐泡时间、密度数据见表1：
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 560D | |
| A-33用量/g | 0.2 | 0.2 | 0.2 | 0.2 | 0.7 |
| 硅油用量/g | 0.25 | 0.25 | 0.25 | 0.25 | 0.4 |
| 吐泡时间 | 1分45秒 | 1分50秒 | 1分52秒 | 1分51秒 | 1分53秒 |
| 密度kg/m<sup>3</sup> | 37.4 | 38.1 | 38.2 | 37.6 | 35.1 |
由表1数据得出，与市场常规的软泡聚醚560D相比，本发明聚醚多元醇可明显减少A33的用量，吐泡时间近似一致，且硅油的用量较少，泡沫密度较高。催化剂用量越少，VOC数值越小。
回弹率、25％压陷、65％压陷数据见表2：
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 560D | |
| 回弹率/％ | 38.5 | 39.5 | 38.9 | 38 | 30.5 |
| 25％压陷 | 127 | 133.5 | 129.5 | 125.8 | 113.5 |
| 65％压陷 | 230.5 | 227.5 | 234 | 238.5 | 199.5 |
海绵气味等级数据见表3：
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 560D | |
| 海绵气味等级 | 3.0 | 3.0 | 3.5 | 3.5 | 4.0 |
注：气味等级，数值越小越好。
Claims (10)
1.一种可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：采用多元醇类化合物、端氨基聚醚或叔胺基有机胺中的一种或几种为起始剂，以碱金属或有机胺为催化剂，与环氧烷烃分两个阶段聚合反应，经过精制，得到自催化软泡聚醚多元醇。
2.根据权利要求1所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：包括以下步骤：
(1)前段聚合反应：首先在反应釜中加入起始剂、催化剂搅拌均匀后，进行氮气置换，测釜内氧含量小于10-300ppm后，抽真空至-0.1～-0.06MPa，升温至90-120℃脱水2-10h，使得水分≦0.1％；开始加入环氧烷烃，保持釜内温度100-120℃，压力0-0.4MPa，进料结束后，内压反应2-6小时，真空脱除未反应完全的环氧烷烃，降温，得中间体聚醚多元醇；
(2)后段聚合反应：将中间体聚醚多元醇、催化剂加入到反应釜中，进行氮气置换，测釜内氧含量小于10-300ppm后，抽真空至-0.1～-0.06MPa，升温至90-120℃脱水2-10h；开始加入环氧烷烃，保持釜内温度100-120℃，压力0-0.4MPa，进料结束后，内压反应2-4小时；抽真空至-0.1～-0.095MPa，110℃氮气鼓泡1h，脱除未反应完全的环氧烷烃单体；聚合完毕，得粗聚醚，加入纯水和吸附剂处理，并在真空下脱水，脱水完毕后对其过滤，得到自催化软泡聚醚多元醇。
3.根据权利要求2所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：所述的中间体聚醚多元醇的分子量为400-2000。
4.根据权利要求1或2所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：所述的自催化软泡聚醚多元醇官能度为2-8，分子量为1000-10000。
5.根据权利要求1所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：所述的多元醇类化合物为甘油、丙二醇、二乙二醇、乙二醇、山梨醇、蔗糖醇、季戊四醇、木糖醇、甘露醇、蔗糖或葡萄糖甙化合物中的一种或几种。
6.根据权利要求1所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：所述的端氨基聚醚是一类具有柔软的聚醚骨架，末端以氨基或胺基封端的化合物，官能度为2-8，数均分子量为200-5000，总胺：2-20。
7.根据权利要求1所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：所述的叔胺基有机胺为脂肪胺类、醇胺类、酰胺类、脂环胺类、芳香胺类、萘系胺类含活泼氢基团的叔胺基有机胺中的一种或几种。
8.根据权利要求1所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：所述的环氧烷烃为环氧乙烷、环氧丙烷或环氧丁烷中的一种或几种。
9.根据权利要求1所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：步骤(1)中，所述的催化剂的用量为起始剂、催化剂和环氧烷烃总量的0.05-0.5％；
步骤(2)中，所述的催化剂的用量为中间体聚醚多元醇、催化剂和环氧烷烃总量的0.05-0.5％。
10.根据权利要求1所述的可用于海绵的自催化软泡聚醚多元醇的制备方法，其特征在于：所述的吸附剂为硅酸镁、硅酸铝或硅酸镁铝中的一种或几种，用量为粗聚醚质量的0.5-2％。
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| CN114085373A (zh) * | 2021-12-09 | 2022-02-25 | 万华化学集团股份有限公司 | 一种透明质酸聚醚多元醇及其制备方法和应用 |
| CN115322358A (zh) * | 2022-08-18 | 2022-11-11 | 上海东大化学有限公司 | 基于环糊精的聚醚多元醇的合成方法 |
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| CN114085373A (zh) * | 2021-12-09 | 2022-02-25 | 万华化学集团股份有限公司 | 一种透明质酸聚醚多元醇及其制备方法和应用 |
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