●366張恩天等,聚酮的合成與性質(zhì)Vol.27. No.6,2005聚酮的合成與性質(zhì)張恩天'，格.別洛夫”， 陳維君，李剛'，石娜1(1.黑龍江省石油化學(xué)研究院,黑龍江哈爾濱150040;2. 俄羅斯科學(xué)院化學(xué)物理問(wèn)題研究所,莫斯科142432)摘要:介紹了以一氧化碳和乙烯為主要原料經(jīng)過(guò)催化共聚合,合成聚酮共聚物的方法以及聚酮共聚物的主要物理、化學(xué)性能。與結(jié)構(gòu)相似的聚乙烯相比,聚酮共聚物具有熔點(diǎn)高.黏附力強(qiáng).較好的光和生物降解性能等優(yōu)點(diǎn)?？衫霉簿畚镏麈溕系聂驶男跃弁簿畚?制成功能高分子材料和具有光活性的高聚物。優(yōu)異的物理、化學(xué)性能和便宜的原材料來(lái)源使得聚酮共聚物的研究和應(yīng)用受到越來(lái)越多的關(guān)注。關(guān)鍵詞:聚酮;-氧化碳;乙烯;洽成;性能中圖分類號(hào):TQ 224.23文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):100 - 0017(2005)06 - 0366 -04Synthesis Method and Properties of PolyketonesZHANC En- tian', C. Belor. CHEN Wei - jun', LI Geang' and SHI Na'(1. Heilongjiang Research Instiute of Petrochemistry, Harbin 150040, China;2. Intitue of Problers of Chemical Physics, RAS, 142432, Chemogoloka, Mosoo Region, Prospect Semenoa,1, Russia)Abstract: Using carbon monoxide and ethylene as raw materials , the synthesis methods and the phyical and chemical properties of polyketones (PK) wereintoduced in this paeper. Carparing with PE, PK copolymers had a lot of advanced propertie such的higher melting termperahure, better adhesion, the psibilityof photo- and bioderadation, the posibility of modifying the copolymerns on the carbonyl groups to prepare functional polymens and 8o on. The authors indicatedthet since the low cot for carbon monoxide and ethylene and the better properties, the inveigation and pplicaion of PK copolymers would be paid muchattention.Key words:polyketone; curbon monoxide; ethylene; aynthesis; property.學(xué)、物理性質(zhì)發(fā)生了很大變化。聚乙烯的性能具有前言許多不足之處,例如熔點(diǎn)較低(≤160C)表面黏附聚酮(Polyketone,簡(jiǎn)為PK) ,這里主要是指分子性差、光或生物降解能力差,而PK共聚物則具有熔主鏈?zhǔn)怯梢蚁┗汪驶湺谓M成的一類高聚物。從點(diǎn)較高 (200 ~ 260C)、較好的表面黏附性和較好的主鏈結(jié)構(gòu)的組成上看,PK共聚物可分為交替共聚物光或生物降解性能,可利用PK共聚物主鏈上的羰和無(wú)規(guī)共聚物兩類,系采用不同的催化劑和反應(yīng)條基改性PK共聚物,制成功能高分子材料和具有光件合成出來(lái)的。PK的合成工藝的研究,早在上個(gè)世活性的高聚物或制成聚螺旋狀縮酮( polyspiroketal)。紀(jì)50年代初即已開始,可通過(guò)乙烯和一氧化碳的自另外,由于PK共聚物的原料采用了價(jià)格便宜、來(lái)源由基共聚、輻照共聚基本流程和催化共聚三種方法充足的一氧化碳,使PK產(chǎn)品的價(jià)格比PE進(jìn)-步降制備。近年來(lái),研究較多的是催化共聚,在釩、鈦催低,為進(jìn)-一步市場(chǎng)開發(fā),創(chuàng)造了良好條件?；瘎┐呋饔孟碌臒o(wú)規(guī)共聚和在鈀催化劑催化作用鑒于PK共聚物具有一系列的優(yōu)點(diǎn),可以將其下的交替共聚。制成纖維、薄膜涂料、工程塑料,也可用作基體樹脂PK交替共聚物結(jié)構(gòu)式如下:制成復(fù)合材料,還可以作為制備其他類型功能高分- (CHCH2CO- CHCH2CO- CH2CH2C0- CH,CH2CO) -子材料的起始材料,其進(jìn)一步的開發(fā)必將具有良好PK無(wú)規(guī)共聚物結(jié)構(gòu)式如下:的經(jīng)濟(jì)效益和社會(huì)效益。- (CH2CH.CH.CHcO - CH.CH2CHCH.CH.CH2CH2CH2CO) -和分子主鏈主要為乙烯基鏈段的聚乙烯、聚丙1 PK共聚物的合成烯相比,由于PK共聚物的主鏈上嵌人了羰基,其化1.1中國(guó)煤化工YHCNMHG收稿日期:2005-05-08作者簡(jiǎn)介:張恩天(1941- ),男,北京市人，研究員,從事合成高分子結(jié)構(gòu)膠黏劑近40年.發(fā)表專業(yè)技術(shù)文獻(xiàn)30余篇.多次成果獲國(guó)家級(jí)省部級(jí)獎(jiǎng)勵(lì)?；瘜W(xué)與黏合2005年第27卷第6期CHEMISTRY AND ADHESION合成PK共聚物的原料主要有一氧化碳和乙以乙烯和一氧化碳交替共聚為例，其反應(yīng)條件烯。可和一氧化碳共聚的單體除了乙烯外還有丙為:聚合溫度40~ 100C,壓力1.0~ 10.0 MPa;反應(yīng)烯異丁烯、高級(jí)a-烯烴、環(huán)戊烯.4-乙烯基環(huán)已釜內(nèi)的漿料由溶劑和均相催化劑組成。溶劑主要為烯苯乙烯和取代苯乙烯。此外還可以采用的共聚甲醇、二氯乙烷、甲苯和少量的水;氣相的成份主要單體有甲基丙烯酸酯、w-十- -烯醇、5-己烯-1-是乙烯和一氧化碳還有少量催化劑、聚酮和--些其醇、3-丁烯-1-醇;w-十一烯酸.6-庚烯酸;己二他成份。烯-1,5、庚二烯-1,6、辛二烯- 1,7;降冰片二烯，乙烯和一氧化碳交替共聚合的基本流程示意圖雙環(huán)戊二烯等。見圖1。1.2合成 PK共聚物的催化劑科學(xué)家從1930年起就開始了乙烯和一氧化碳2 PK共聚物的性能催化共聚合的研究,已經(jīng)研制出--系列共聚合用的2.1PK共聚物中一氧化碳含量對(duì)共聚物熔點(diǎn)的催化劑。交替共聚和無(wú)規(guī)共聚采用的催化劑的種類影響是不一樣的。交替共聚一般采用鈀系催化劑;無(wú)規(guī)PK共聚物中一氧化碳含量對(duì)共聚物熔點(diǎn)的影共聚一般采用釩鈦或鋁系催化劑。各種催化劑、共響,總的來(lái)說(shuō)是--氧化碳含量越高,共聚物的熔點(diǎn)聚反應(yīng)條件和產(chǎn)率見表1。(Tm)也隨之升高,見圖2。表1一氧化碳和乙烯交替共聚合的催化劑、反應(yīng)條件和產(chǎn)率Table 1 The catalysts, reaction conditions and yield for the alemating220copolymerization of co and CH共聚合反應(yīng)條件產(chǎn)率200催化體系聚合溫度/心 聚合用溶劑 聚合壓力M lewh(ByP)AHC212)-210乙睛、苯,乙醇45~- 200616075-125乙腈吡啶2.5-15(Mt)2HC275-15140表2乙烯和一氧化碳無(wú)規(guī)共聚合的催化劑、反應(yīng)條件和產(chǎn)率Table 2 The catalysts, reaction conditions and yield forthe random copolymerization of CO and C2H434350C0/%聚合湘度/心 聚合用溶劑聚合壓力/Mh I圍2 PK 共聚物中一氧化碳含與共聚物熔點(diǎn)的關(guān)系Ta4- A(ioBus0-200辛烷0.02-1010~40Fig.2 Effect of the content of co in PK copolymers on the meltingVO(R)2.v0Q3已烷).1>100point o the copolymers2.2脂肪鏈PK三元共聚物在23C下于各種水溶T(OBu),AIRC240-80庚烷03-1.0從表1和表2可以看出,交替共聚合反應(yīng)的溫液中浸泡一年后,質(zhì)量、體積和屈服點(diǎn)抗張強(qiáng)度的變度、壓力均較高,而產(chǎn)率較低;無(wú)規(guī)共聚合反應(yīng)的溫化見表3。表3脂肪鏈K三元共聚物23C下于各種水溶液中浸泡一年后性能的變化度、壓力均較低,但產(chǎn)率很高。Table 3 The properties changes of neat aliphatic1.3合成 PK共聚物的反應(yīng)條件和基本流程PK terpolymer afer inmersing in aqueous fluids at 23C質(zhì)量變化率體積變化率屈服點(diǎn)抗張強(qiáng)度水溶液制劑%/9的變化率/%10% NaCl水溶液0-反30%NaC水溶液應(yīng)- H真心分司-干爆]-造檢成治10%ZunCh 水溶液催化劑。5%醋酸水溶液10%次-氧化膜1乙.樓上J。強(qiáng)化州5%亞硫中國(guó)煤化工培劑40%亞礦YHCNMHG.圍1合成PK共聚物的基本流程10%羥氨水溶液Fig.1 Principal technologcal scheme of the proces for10%NaOH水溶液preparation of altemating copalymers of Co and CH42.3脂肪鏈PK三元共聚物耐各種車用液體的性能368張恩天等,聚酮的合成與性質(zhì)Vol.27. No.6,2005脂肪鏈PK三元共聚物耐各種車用液體的性能表6脂肪鏈PK共聚物和尼龍66同時(shí)浸泡在80C的幾種見表4。水溶液中,25d后其抗張強(qiáng)度的變化(在23C下測(cè)試)表4脂肪鏈PK三元共聚物耐各種車用液體的性能試驗(yàn)結(jié)果Table 6 Yield stress values for aliphatic PK and polyamide 66 aferTable 4 The properies changes of neat aliphatic PK terpolymerimmersing in various aqueous solution at 80C 25days ( Tensile testsafter immersing in automotive fluidswere at 23C)車用液體名稱浸泡溫度浸泡時(shí)間屈服點(diǎn)抗張強(qiáng)有侵蝕性物質(zhì)的水溶液直鏈聚酮的抗尼龍 66的抗/9/年度的變化/%張強(qiáng)度/MPa___ 張強(qiáng)度/MPa23起始值(相對(duì)濕度50%)57.957.2無(wú)鉛汽油59.233.1酒精-汽油混合燃料M-1510%重份的NaOH水溶液60.028.9-1%重份的NaOH水溶液58.628.2含10%乙醇、甲醇的酒精-4510%重份的HCl水溶液64.7溶解汽油混合燃料-11%重份的HCI水溶液59.3變脆030%重份的H2SO4 水溶液電機(jī)潤(rùn)滑油1550%重份的ZnCh水溶液46.2海水60.2底盤潤(rùn)滑油105%重份的HAe水溶液33.81%重份的CaCh水溶液35.8傳動(dòng)液防凍液2.6脂肪鏈PK共聚物和幾種其它共聚物,在不同Skyddl 500 B11相對(duì)濕度時(shí)于23下的氧阻礙系數(shù)的對(duì)比見表7。表7脂肪鏈PK共聚物和幾種其它共聚物在不同相對(duì)濕度100%防凍掖- 10時(shí)于23C下的氧阻礙系數(shù)的對(duì)比Table 7 Oxygen permeability cofficients for several barrier50%防凍掖polymers at 23C and diferent relative humidity聚合物ORH75RH90RH含水50%的硫酸電池液聚對(duì)苯二甲酸乙二醇酯(PET)3.43.53.52.4聚酮浸泡在 80C的各種溶劑中,25 d后其屈服尼龍661.82.04.5乙烯-乙烯醇共聚物P(E - EVA)0.090.11 0.35應(yīng)力值和質(zhì)量增加值的變化見表5。脂肪族聚酮(PK)0.10.30.9表5脂肪鏈聚酮浸泡在 80C的各種溶劑中,25 d后其屈服2.7脂肪鏈PK共聚物和幾種其它聚合物的熱性應(yīng)力值和質(zhì)量增加值的變化能密度以及自由體積分?jǐn)?shù)的對(duì)比見表8。.Table 5 Yield stress values and percentage weight for aliphatic PK表8 K共聚物和幾種其它聚合物的熱性能、密度以及自 由體積分?jǐn)?shù)afer immersing in various organic solvents at 80C for 25 daysTable 8 Thermal properties, density and fractional fre( yield stress tests were at 23c)volume for aliphatic PK and several polymeric materials質(zhì)量增加值屈服應(yīng)力值溶劑/%/MPa豪合物密度 無(wú)定形度 自由體積分?jǐn)?shù)2.5脂肪族聚酮202351.09.:55.1414.2甲醇53.1襄財(cái)輩二甲酸丁二酶商(Bsr).321.2乙醇4.256.9囊對(duì)苯二甲酸乙二酶嘴(ET).41.乙酸乙酯3.7.910.818.0甲乙酮4.63794_0.汽油62.02.8脂肪族PK三元共聚物在23C時(shí)在各種應(yīng)力三氧乙烯8.055.1二氧甲烷35.038.6作用下的應(yīng)力蠕變表觀模量見表9。氯仿32.040.0中國(guó)煤化工3二甲基亞砜15.945.5MHCNMHG2.5PK共聚物和尼龍66同時(shí)浸泡在80C各種有Pk共策物田丁具有優(yōu)開時(shí)物理、化學(xué)性能,近侵蝕性物質(zhì)的水溶液中,25 d后其抗張強(qiáng)度的變化年來(lái)越來(lái)越引起人們的重視。雖然從.上個(gè)世紀(jì)30見表6。.年代起即有人開始了聚酮的研究工作,但在1991年化學(xué)與黏合2005 年第27眷第6期CHEMISTRY AND ADHESION●369.表9脂肪鏈PK三元共聚物239C時(shí)在各種應(yīng)力作用下的Caalysis loday, 199,48.(1-4):49- 56.表觀應(yīng)力蠕變模量[7] DMITRII M SHKRABO. 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