CN1721461A - 制备基于已二醇醚碳酸酯的澄清异氰酸酯预聚物 - Google Patents
制备基于已二醇醚碳酸酯的澄清异氰酸酯预聚物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/40—Post-polymerisation treatment
- C08G64/406—Purifying; Drying
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- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明提供一种制备澄清,可稳定储存的异氰酸酯-封端预聚物的方法。这种异氰酸酯-封端预聚物基于己二醇醚碳酸酯。本发明还涉及由这些异氰酸酯-封端预聚物制备聚氨酯的方法。
Description
技术领域
本发明涉及制备基于聚碳酸酯多元醇的异氰酸酯预聚物的改善方法,其中预聚物不出现混浊。
背景技术
根据现有技术,将基于己二醇醚的聚碳酸酯多元醇与摩尔过量多异氰酸酯,通常为4,4′-二苯甲烷二异氰酸酯反应,生成具有末端NCO基团的异氰酸酯预聚物(″NCO预聚物″)。这些异氰酸酯预聚物是制备聚氨酯可浇注(pourable)弹性体的重要原材料。
这些NCO预聚物,特别是那些基于4,4′-二苯甲烷二异氰酸酯以及己二醇醚碳酸酯多元醇的预聚物的缺点是,通常它们在室温下储存时迅速变为混浊,甚至可以形成一种半结晶沉降物。提高NCO预聚物的贮存温度使NCO预聚物的粘度大大增加,并且最终导致预聚物失去效用。如果将曾经冷却过,并且因此显示出浊度或沉降物的NCO预聚物重新加热,也会出现同样的情况。在进一步反应期间,沉积物使得到的浇注(poured)弹性体性质不均匀。这些性质不均匀反过来又可以导致弹性体材料损坏。
发明内容
本发明目的是提供一种制备这些NCO预聚物的方法,作为技术改进的结果,预聚物将不再混浊。现在发现可以制备即使在室温下长时间储存仍然澄清,不会出现混浊的NCO预聚物。这种方法需要在与多异氰酸酯反应之前,将聚碳酸酯多元醇进行短路或薄膜蒸馏,以迅速除去其中在压力为0.1mbar时沸点低于200℃的挥发性成分。
本发明提供一种制备澄清并且在室温下可稳定储存的NCO-封端预聚物的方法。这种方法包括将聚碳酸酯多元醇与化学计量过量的4,4′-二苯甲烷二异氰酸酯反应,其中在反应之前将聚碳酸酯多元醇进行短路或薄膜蒸馏。这种短路或薄膜蒸馏使聚碳酸酯多元醇的羟值减少了至少1.5羟值单元,优选至少3羟值单元。
在这里使用时,短语″澄清并且在储存时稳定″的意思是即使在23℃下储存三个星期后,预聚物也不出现任何浊度,并且预聚物的NCO基团含量也不出现显著变化。
在本领域的技术人员熟知的装置中通过蒸馏减少聚碳酸酯多元醇的羟值。合适的装置包括例如降膜式蒸发器,薄膜式蒸发器以及分子蒸发器。优选以连续方式进行蒸馏。蒸馏优选在温度160至250℃,优选180至210℃,压力0.05至10mbar,优选0.1至3mbar下进行。在温度为40至100℃范围内选择的指形冷凝管中以液态形式分离馏出液。可以再次利用所分离的馏出液制备聚碳酸酯多元醇。聚碳酸酯多元醇在蒸馏器中的平均停留时间优选为2至600s。
在连续地注入蒸发设备前,可以方便地用换热器加热聚碳酸酯多元醇。在优选的实施方案中,在聚碳酸酯多元醇的制备过程后紧接着通过蒸馏处理聚碳酸酯多元醇,因为在最后生产阶段,聚碳酸酯多元醇通常为接近200℃。因此,没有进一步的能量消耗。紧接着离开蒸馏器后,将聚碳酸酯多元醇冷却至低于120℃的温度。根据馏出液的组成,一般情况下将馏出液的冷凝器加热至50至75℃温度范围内。此外,在减压下操作蒸馏器以提高运行有效。这时,正常的压力是低于100mbar,优选地低于20mbar。可以向聚碳酸酯多元醇添加所谓的夹带剂以进一步地提高效率。用作所谓的夹带剂的合适的材料包括少量沸点在100至300度范围内的惰性溶剂。诸如环丁砜、甲苯或二甲苯的为本领域的技术人员所知的物质可以用作夹带剂。
取决于其效率,聚碳酸酯多元醇的蒸馏可以减少大约1.5至大约15羟值单元,并且优选地大约3至大约8羟值单元。
然后以本领域的技术人员所知的方式,将通过蒸馏进行预处理的聚碳酸酯多元醇与化学计量过量的4,4′-二苯甲烷二异氰酸酯(可从Bayer AG商购得到)在高温(通常在50至100℃范围内)下反应,以制备具有一个或多个终端NCO基团的预聚物。在本发明方法中使用的聚碳酸酯多元醇一般具有27至113mgKOH/g的羟值(也就是OH数)。根据本发明制备的预聚物一般情况下NCO基团含量为5至15wt.%NCO。
下列实施例进一步详细解释本发明的方法。不能通过这些实施例限制在上述说明中阐明的本发明的精神或范围。本领域的技术人员可以很容易地理解可以对下列方法的条件进行已知的变化。除非另作说明,所有温度都是以摄氏温度表示,所有百分数都表示重量百分数。
具体实施方式
实施例
实施例1
聚碳酸酯多元醇的制备:
将9000g可商购基于羟值为53mgKOH/g的己二醇醚的聚碳酸酯多元醇与101g 1,6-己二醇混合,然后在200℃下退火14小时。所形成的聚碳酸酯多元醇OH值是63.7mg KOH/g,并且所形成的聚碳酸酯多元醇的粘度是840mPas(75℃)。
实施例2
聚碳酸酯多元醇的制备:
将3900g羟值为535mg KOH/g的己二醇醚,725g己二醇与4635g碳酸联苯酯以及150mg氧化二丁基锡在180℃、标准大气压下加热1小时。冷却至110℃,降低压力至15mbar,开始蒸馏苯酚。在10小时内将温度升至200℃。将压力降低至0.5mbar,保持1小时以完成反应。所形成的聚碳酸酯多元醇OH值是62.5mgKOH/g,并且所形成的聚碳酸酯多元醇的粘度是910mPas(75℃)。
实施例3
对根据本发明实施例1制得的聚碳酸酯多元醇的处理:
将8900g实施例1中制得的聚碳酸酯多元醇预热至160℃,并且在<1mbar的压力下将其进行短路蒸发6小时。在200℃下操作预蒸发器,夹套温度同样是200℃,在温度为50℃的指形冷凝管内凝聚馏出液。在维持恒温为10℃的收集容器内收集除去了馏出液的聚碳酸酯多元醇。
制得的8676g聚碳酸酯多元醇的OH值为56.6mg KOH/g,粘度为890mPas(75℃),以及108gOH值为495mgKOH/g的馏出液。
实施例4
对根据本发明实施例2制得的聚碳酸酯多元醇的处理:
将4820g实施例2中制得的聚碳酸酯多元醇预热至160℃,并且在<2mbar的压力下将其进行短路蒸发3小时。在200℃下操作预蒸发器,夹套温度同样是200℃,在温度为50℃的指形冷凝管内凝聚馏出液。在维持恒温为10℃的收集容器内收集除去了馏出液的聚碳酸酯多元醇。
制得的4696g聚碳酸酯多元醇的OH值为55.2mg KOH/g,粘度为1000mPas(75℃),以及74gOH值为465mgKOH/g的馏出液。
实施例5
用实施例3得到的聚碳酸酯多元醇制备NCO-封端预聚物:
将2802g实施例3制得的聚碳酸酯多元醇添加到50℃、放置于氮气中的1698g 4,4′-二苯甲烷二异氰酸酯(可从Bayer AG商购得到)中,在80℃下搅拌混合物2小时。测得产物NCO含量是9.96wt.%NCO,以及70℃下粘度是1620mPas。刚制备得到的最终产品(也就是NCO封端预聚物)是完全澄清的。同样地,在室温下将制得的预聚物储存21天也未观察到混浊。
实施例6
用实施例4得到的聚碳酸酯多元醇制备NCO-封端预聚物:
将2810g实施例4制得的聚碳酸酯多元醇添加到50℃、放置于氮气中的1690g 4,4′-二苯甲烷二异氰酸酯(可从Bayer AG商购得到)中,在80℃下搅拌混合物2小时。测得产物NCO含量是10.01wt.%NCO,以及70℃下粘度是1625mPas。刚制备得到的最终产品,也就是NCO封端预聚物,是完全澄清的。同样地,在室温下将制得的预聚物储存21天也未观察到混浊。
实施例7:
对比例:将1366kg OH值为58mg KOH/g基于己二醇的聚碳酸酯多元醇(可从Bayer AG商购得到)添加到50℃、放置于氮气中的834kg 4,4′-二苯甲烷二异氰酸酯(可从Bayer AG商购得到)中,在80℃下搅拌混合物2小时。测得产物NCO含量是9.97wt.%NCO,以及70℃下粘度是1880mPas。刚制备得到的最终产品(NCO-封端预聚物)显示出轻微混浊。在室温下将预聚物储存2天后,观察到浊度继续增加,储存4个月后沉降不断增加。
虽然已为了说明的目的在前面详细描述了本发明,但是需要理解的是,此类细节仅仅为了该目的,在不脱离由权利要求限定的精神和范围的前提下可由所属技术领域中的技术人员作各种变化。
Claims (2)
1.一种制备澄清并且在室温下可稳定储存的NCO-封端预聚物的方法,包括
(A)将(1)一种或多种聚碳酸酯多元醇,
与
(2)化学计量过量的4,4′-二苯甲烷二异氰酸酯反应,其中在与4,4′-二苯甲烷二异氰酸酯反应之前将(1)聚碳酸酯多元醇进行短路或薄膜蒸馏处理,以使聚碳酸酯多元醇的羟值减少至少1.5羟值单元。
2.一种制备聚氨酯的方法,包括将(I)至少一种多异氰酸酯组分与(II)至少一种异氰酸酯-反应性组分反应,改进之处在于其中(I)所述多异氰酸酯组分包括由权利要求1所述方法制备的NCO-封端预聚物。
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Application Number | Priority Date | Filing Date | Title |
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DE102004032419.0 | 2004-07-05 | ||
DE102004032419A DE102004032419A1 (de) | 2004-07-05 | 2004-07-05 | Herstellung klarer Isocyanatprepolymere auf Hexandiolethercarbonat-Basis |
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CN1721461A true CN1721461A (zh) | 2006-01-18 |
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CNA2005100837089A Pending CN1721461A (zh) | 2004-07-05 | 2005-07-05 | 制备基于已二醇醚碳酸酯的澄清异氰酸酯预聚物 |
Country Status (7)
Country | Link |
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US (1) | US20060004172A1 (zh) |
EP (1) | EP1614702A1 (zh) |
JP (1) | JP2006022330A (zh) |
CN (1) | CN1721461A (zh) |
BR (1) | BRPI0502630A (zh) |
DE (1) | DE102004032419A1 (zh) |
MX (1) | MXPA05007259A (zh) |
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KR101980408B1 (ko) | 2011-12-20 | 2019-05-20 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 하이드록시-아미노 중합체 및 그의 제조 방법 |
US9890243B2 (en) | 2014-10-29 | 2018-02-13 | Resinate Materials Group, Inc. | Polymeric plasticizer compositions |
US9580546B2 (en) | 2014-10-29 | 2017-02-28 | Resinate Materials Group, Inc. | Polymeric plasticizer compositions |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2294199A1 (fr) * | 1974-12-11 | 1976-07-09 | Poudres & Explosifs Ste Nale | Procede perfectionne de preparation de polycarbonates en deux etapes |
DE3717060A1 (de) * | 1987-05-21 | 1988-12-01 | Bayer Ag | Polyether-polycarbonat-diole, ihre herstellung und verwendung als ausgangsprodukte fuer polyurethankunststoffe |
DE3855663T2 (de) * | 1987-08-04 | 1997-06-05 | Asahi Chemical Ind | Copolycarbonate |
US4837292A (en) * | 1987-12-17 | 1989-06-06 | E. I. Dupont De Nemours And Company | Article of spandex having polycarbonate soft segment |
DE3932949A1 (de) * | 1989-10-03 | 1991-04-11 | Bayer Ag | Elasthanfasern hoher dehnbarkeit und festigkeit und ein verfahren zu ihrer herstellung |
JPH0450281A (ja) * | 1990-06-15 | 1992-02-19 | Sunstar Eng Inc | シーリング材組成物 |
DE4223014A1 (de) * | 1992-07-13 | 1994-01-20 | Bayer Ag | Verfahren zur Herstellung foggingarmer Polyesterpolyurethane-Weichschaumstoffe und ihre Verwendung in Verkehrsmitteln |
US5962619A (en) * | 1998-03-16 | 1999-10-05 | Arco Chemical Technology, L.P. | Process for making clear polyurethane/urea elastomers |
ES2217084T3 (es) * | 2000-12-26 | 2004-11-01 | Ube Industries, Ltd. | Poliuretano termoplastico. |
WO2002070584A1 (fr) * | 2001-03-01 | 2002-09-12 | Asahi Kasei Kabushiki Kaisha | Diol copolycarbonate et polyurethane thermoplastique obtenu a partir de ce dernier |
-
2004
- 2004-07-05 DE DE102004032419A patent/DE102004032419A1/de not_active Withdrawn
-
2005
- 2005-06-22 EP EP05013449A patent/EP1614702A1/de not_active Withdrawn
- 2005-06-29 US US11/170,615 patent/US20060004172A1/en not_active Abandoned
- 2005-07-01 MX MXPA05007259A patent/MXPA05007259A/es unknown
- 2005-07-04 BR BRPI0502630-0A patent/BRPI0502630A/pt not_active Application Discontinuation
- 2005-07-04 JP JP2005194956A patent/JP2006022330A/ja active Pending
- 2005-07-05 CN CNA2005100837089A patent/CN1721461A/zh active Pending
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Publication number | Publication date |
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US20060004172A1 (en) | 2006-01-05 |
MXPA05007259A (es) | 2006-01-11 |
JP2006022330A (ja) | 2006-01-26 |
BRPI0502630A (pt) | 2006-02-14 |
EP1614702A1 (de) | 2006-01-11 |
DE102004032419A1 (de) | 2006-01-26 |
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