低不饱和度超高分子量聚醚多元醇的合成研究

以聚醚二醇为起始剂,环氧丙烷(PO)为主原料,使用双金属络合催化剂(DMC)合成低不饱和度相对分子质量约为12 000的聚醚二醇。讨论了起始剂分子量、DMC含量、PO加料速率、搅拌转速及反应温度对制得聚醚的黏度、不饱和度和分子量分布的影响。结果表明,以DDL-6000D为起始剂、DMC质量分数为50×10~(-6)、PO加料速率3.96～4.37 mol/(L·h)、搅拌转速300 r/min、反应温度(145±5)℃时,可制得黏度低、不饱和度低、分子量分布指数小的聚醚产品。     

高级脂肪醇基聚醚一元醇的合成研究

以高级脂肪醇为起始剂,双金属氰化物络合物(DMC)为催化剂合成了一种分子量约2 100 g/mol的聚醚一元醇。讨论了起始剂水分、起始剂种类、环氧丙烷(PO)进料速率、聚醚中引入的环氧乙烷(EO)含量、环氧烷烃(PO/EO)共聚方式等条件对聚合反应活性以及产物性能的影响。结果表明,起始剂水分宜控制在0.04%以下;起始剂结构和种类、PO进料速率、PO/EO共聚方式都会对聚醚一元醇性能产生影响;合成的聚醚一元醇具有分子量分布窄、不饱和度低、浊点可调等特点。     

水溶性淬火剂用共聚醚的合成研究

研究了以ＫＯＨ为催化剂，二元或三元醇为起始剂，采用阴离子开环聚合合成淬火剂用共聚醚。结果表明：产物的分子量随起始剂和杂质量的减少而增加；聚醚的组成取决于投料比；其浊点随环氧乙烷含量增加而升高。起始剂用量≤８．０ｍｍｏｌＯＨ／１００ｇ单体；反应温度以１０５±５℃为宜；单体水分含量＜０．１％，醛含量＜０．１７％，环氧乙烷含量为８０±３ｍｏｌ％，合成的共聚醚分子量可大于１．０×１０４。     

组合聚醚GX－101及其生产工艺

在碱性催化剂的作用下，含活泼氢的起始剂与氧化烯烃开环聚合反应。在一定的温度和压力下制得分子量５００－１０００的聚醚多元醇，并与泡沫稳定剂、催化剂等助剂复配成组合聚醚。组合聚醚再与异氰酸酯反应得到硬质聚氨酯泡沫。     

组合聚醚GX—101及其生产工艺

在碱性催化剂的作用下，含活泼氢的起始剂与氧化烯烃开环聚合反应。在一定的温度和压力下制得分子量５００－１０００的聚醚多元醇，并与泡沫稳定剂、催化剂等助剂复配成组合聚醚。组合聚醚再与异氰酸酯反应得到硬质聚氨酯泡沫。     

低黏度高相对分子质量聚醚三醇的合成及应用

以低相对分子质量聚醚三醇为起始剂,使用自产聚醚催化剂TMD催化环氧丙烷(PO)开环聚合制备低黏度高相对分子质量聚醚多元醇。讨论了起始剂种类、TMD含量、PO预投量对聚醚三醇性能的影响。结果表明,选用MN-1000做起始剂、TMD催化剂质量分数为35×10~(-6)(占总投料量)、PO预滴量为起始剂质量的12%时,得到黏度为2120 m Pa·s(25℃)、相对分子质量分布指数(D值)为1.07、不饱和值为6.4 mmol/kg、相对分子质量8000左右的聚醚三醇。用其制备的减震用聚氨酯铺装材料的断裂伸长率和回弹率均较高。     

国外聚氨酯泡沫塑料工业(连载)

Ⅱ.聚醚聚醚,是聚氨酯泡沫塑料主要原料之一。一般是以多元醇、多元胺或其他含活泼氢的有机化合物为起始剂,与氧化烯烃开环聚合而成。软质聚氨酯泡沫塑料用的聚醚,起始剂为二元醇、三元醇,硬质聚氨酯泡沫塑料用的聚醚,起始剂为三元醇以上的多元醇或多元胺类,例如甘油三羟甲基丙烷、季戊四醇、山梨醇和蔗糖等。软质聚氨酯泡沫塑料用的聚醚羟值比较低,通常在40～60毫克KOH/克左右。而聚氨酯硬质泡沫塑料使用的聚醚羟值较高,在400～600     

GPC法测定纺织油剂聚醚的分子量分布

采用岛津双凝胶色谱柱体系建立了一套适用于纺织油剂聚醚（Ｍ＝１００～１００００）分子量分布分段测定的ＧＰＣ新方法，用该法对国产１５个样品进行分析，结果表明，质量较好的样品，都较低，且服从泊松分布，反之则质量较差。以酸为起始剂的聚醚分子量分布较窄。油剂聚醚的质量与其结构（起始剂种类和聚合度等）有关。     

聚醚型原油破乳剂结构与破乳性能关系的研究

以直链和支链结构的醇类、胺类以及稠环树脂为起始剂,通过烷氧基化反应合成了一系列嵌段聚醚型破乳剂。针对新疆塔河油田原油,讨论了聚醚破乳剂的起始剂类型、支化结构、起始剂含量、环氧乙烷与环氧丙烷质量比值[m(EO)/m(PO)]以及嵌段结构和方式对其脱水效果的影响。结果表明,针对新疆塔河油田原油,合成的多分枝型聚醚破乳剂脱水效果较好;聚醚破乳剂的起始剂质量比在0.3%～1.5%,HLB值在9.5～11.5,破乳脱水效果较好;末端为PEO嵌段的二嵌段聚醚破乳剂脱水速率快,脱水率最高;多嵌段结构聚醚破乳剂脱水速度较慢,但分离出的水色清,污水含油率低。     

聚醚大单体合成工艺的研究进展

经过近一个世纪的发展,聚醚大单体的生产工艺已经成熟:以不同结构的小分子不饱和醇作为起始剂,催化剂与起始剂混合后用氮气置换,体系中通入环氧乙烷进行乙氧基化反应,反应结束后经脱水过滤得到聚醚单体。本文从起始剂、嵌段改性以及催化剂等几个方面,介绍了聚醚大单体合成工艺的研究进展。     

Use of gas-liquid chromatography in the analysis of rigid polyurethane foam polyols

Detailed characterization of the low molecular weight polyols used as intermediates in rigid polyurethane foam production has not been feasible to date. Gas-liquid chromatography of the trimethylsilyl ether derivatives of the polyols now offers a more complete picture of polyol composition, particularly with regard to the molecular weight distribution. The data may be interpreted on a semiquantitative basis. The study of processing variables in polyol manufacture, detection of impurities and analysis of unknown polyols or those based on mixed initiators may all be facilitated by use of this GLC technique.     

Study of cryostructuration of polymer systems. XI. The formation of PVA cryogels by freezing–thawing the polymer aqueous solutions containing additives of some polyols

The influence of the presence of some polyols in initial poly(vinyl alcohol) aqueous solutions on rheological and thermal properties of the cryogels, which were produced by the freezing–thawing method, was investigated. The polyol additives (cosolvents) were as follows: glycerol, propylene glycol, mono-, di-, and triethylene glycols, and oligoethylene glycols (PEG-400 and PEG-1000). It was shown that the introduction of glycerol, propylene, or ethylene glycols into the polymer solution resulted in a decrease of cryogel's shear modulus and fusion temperature, whereas the use of triethylene and higher ethylene glycol oligomers as cosolvents gave rise to an increase in the gel's strength and thermostability, and diethylene glycol exhibited a transitional influence. The possible mechanism of the action of reinforcing cosolvents is discussed. © 1995 John Wiley & Sons, Inc.     

DMC催化剂和生产低不饱和度聚醚的研究进展

介绍了使用DMC催化剂生产低不饱和度聚醚时存在的问题。采用真空汽提/惰性气体吹扫相结合的方法处理催化剂、起始剂混合物,采用全氟烷基磺酸金属盐作催化剂合成低相对分子质量聚醚多元醇起始剂,使用含酮配位体的DMC催化剂、向反应釜内连续添加低分子多元醇起始剂和催化剂等方法是缩短诱导期、降低极高相对分子质量聚醚多元醇含量之有效途径,也可提高反应器的生产效率。     

低不饱和度高活性聚醚多元醇的研制

使用双金属氰化物络合催化剂,首先制备了低不饱和度高相对分子质量聚氧化丙烯多元醇,再采用碱金属化合物催化剂,用环氧乙烷封端,制得高活性聚醚多元醇,所得聚醚二醇及聚醚三醇的羟值约为26mgKOH/g,不饱和度约0.007mmol/g,伯羟基摩尔分数大于85％。     

聚己内酯多元醇的合成与表征

分别以乙二醇、三羟甲基丙烷和季戊四醇为起始剂,经ε-己内酯开环聚合制备了一系列聚己内酯多元醇。探讨了反应温度、时间和催化剂等因素对合成反应的影响,并采用红外光谱(FTIR)、羟值滴定、凝胶渗透色谱(GPC)对聚己内酯多元醇进行了表征。结果表明,以无水乙酸锌为催化剂,且用量为己内酯单体摩尔分数的0.2%,在温度120℃条件下反应3~4 h,制备的多元醇为理想的聚己内酯多元醇,相对分子质量与设计值一致,而且具有相对分子质量分布窄、成本低的特点。     

Synthesis of new free‐radical initiators for polymerization

Synthesis and properties of new initiating systems formed from commercially available ketones, glycols, and hydrogen peroxide (60%) are presented. In preparation of free radical initiators methyl ethyl ketone, which was oxidized by hydrogen peroxide, was used. Reaction was carried out in etanodiol or 1,4‐butanodiol as diluent. The obtained initiators with cobalt octoate as a promotor were applied for crosslinking of the commercially available unsaturated polyester resin. Properties of the resin were compared with those obtained while it was hardened by the typical curing system containing methyl ethyl ketone hydroperoxide and cobalt octoate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2238–2243, 2003     

Synthesis and reactivity of Mannich-derived polyoxyethylene amines as epoxy curing agents

The facile Mannich reaction of phenol, formaldehyde, and polyoxyalkylene polyamines at various molar ratios afforded a family of polyetheramines containing functionalities of phenol, primary amines, secondary amines, and polyoxyethylene or polyoxypropylene block copolymers in the same molecule. The synthesis can be generalized by using various polyoxyethylene or polyoxypropylene diamines (and triamines) of molecular weights ranging from 104 to 430 to prepare a family of Mannich amines, with exception of certain gel products such as phenol/formaldehyde/bis(aminoethyl)ether adduct at 1 : 3 : 3 molar ratio. The series of Mannich amines were evaluated for their epoxy curing reactivities by comparing their gel time and drying time. The Mannich amines prepared from polyoxyethylene amines exhibited higher reactivities than those of polyoxypropylene amine derivatives. The trend of their relative reactivities is explained by the molecular size, the multiplicity of amines in the molecule, and the steric hindrance of amine structure. The physical properties of cured epoxy materials, such as impact, tensile, flexural strength, and hardness properties were also measured and correlated with the amine molecular weight, crosslinking density, and the presence of phenol group. The structure–property relationship is discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2339–2346, 1997     

Degradable polyurethane based on star-shaped polyester polyols (trimethylolpropane and ɛ-caprolactone) for marine antifouling

The star-shaped polyester polyols based on initiators (trimethylolpropane or pentaerythritol) and ɛ-caprolactone were prepared by polycondensation reaction. The degradable polyurethane (PU) films were prepared by mixing star-shaped polyester polyols and crosslinker agent (hexamethylene diisocyanate trimer). The hydrolytic degradation and water absorption experiments demonstrated that the PU films could erode in artificial sea water, which were controlled by varying the ratios of ɛ-caprolactone/trimethylolpropane and the arm number of star-shaped polyester polyols. The mechanical properties of PU films and coatings increased with decreasing the ratios of ɛ-caprolactone/trimethylolpropane and increasing the arm number of star-shaped polyester polyols. The surfaces of PU films and coatings kept eroding, which were revealed by scanning electron microscopy. The copper ion release rates from PU coatings reached steady state at about 31 days. The marine field tests of PU coatings demonstrated that the degradable PU coatings based on star-shaped polyester polyols were effective coatings for marine antifouling.     

松香基表面活性剂研究进展

松香是一类产量丰富、价格低廉的可再生林产资源,被广泛地应用于食品、农业、橡胶、油墨、涂料等领域。松香的三环二萜结构具有超强的疏水性,通过催化异构、Diels-Alder加成等手段引入亲水基团可制备高附加值、易生物降解的绿色表面活性剂。本文从阴离子、阳离子、非离子和两性离子表面活性剂4个大类对松香基表面活性剂应用的文献及专利进行综述,重点分析了羧酸盐、磺酸盐、硫酸盐和磷酸盐4种阴离子型表面活性剂和季铵盐阳离子型表面活性剂,多元醇型和聚氧乙烯型非离子表面活性剂,以及甜菜碱型和氧化胺型两性离子表面活性剂。剖析松香基表面活性剂产业化开发的新技术及新产品概况,提出松香基表面活性剂替代传统表面活性剂的潜在应用领域。同时,对松香基表面活性剂的研究发展与产业化发展进行了评价与展望。     

Molecular weight advancement of poly(ethylene ether carbonate) polyols

Poly(ethylene ether carbonate) polyols have been prepared from ethylene carbonate and monoethylene glycol (MEG) or diethylene glycol (DEG) using sodium stannate trihydrate as catalyst. When these polyols (catalyst removed) are heated to elevated temperatures (< 180°C) at reduced Pressures, volatile impurities are removed, as distillate, molecular weight builds in a controllable manner. This is thought to be a transesterification process in which ? OC(O)CH₂CH₂OCH₂CH₂OH end groups on one molecule react with carbonate moieties on a second molecule with loss of DEG. These advanced polyols form rapidly with high CO₂ retention and relatively low polydispersity. This process has been characterized by size exclusion chromatography, quantitative capillary gas chromatography of the distillates, ¹³C-NMR of the products, and alkaline hydrolysis of the products followed by quantification of the resultant glycols. The advanced polyols are largely alternating copolymers of DEG and CO₂. They are valuable polyols for polyurethane fabrication.