CN106467607B - 聚碳酸酯二醇及使用该聚碳酸酯二醇制得的热塑性聚氨酯 - Google Patents
聚碳酸酯二醇及使用该聚碳酸酯二醇制得的热塑性聚氨酯 Download PDFInfo
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- CN106467607B CN106467607B CN201510705406.4A CN201510705406A CN106467607B CN 106467607 B CN106467607 B CN 106467607B CN 201510705406 A CN201510705406 A CN 201510705406A CN 106467607 B CN106467607 B CN 106467607B
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- glycol
- alkylidene
- polycarbonate glycol
- polycarbonate
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 44
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 44
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 15
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- 150000002009 diols Chemical class 0.000 title abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 96
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 47
- -1 formula (A) Chemical compound 0.000 claims description 19
- 125000001118 alkylidene group Chemical group 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003252 repetitive effect Effects 0.000 claims description 5
- JISVIRFOSOKJIU-UHFFFAOYSA-N hexylidene Chemical group [CH2+]CCCC[CH-] JISVIRFOSOKJIU-UHFFFAOYSA-N 0.000 claims description 3
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 13
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- 238000012360 testing method Methods 0.000 description 10
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- 238000000034 method Methods 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229940043375 1,5-pentanediol Drugs 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
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- 125000001931 aliphatic group Chemical group 0.000 description 3
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical class [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
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- ZJWDJIVISLUQQZ-UHFFFAOYSA-N 2,4-dimethylpentane-1,5-diol Chemical compound OCC(C)CC(C)CO ZJWDJIVISLUQQZ-UHFFFAOYSA-N 0.000 description 1
- ZOAMZFNAPHWBEN-UHFFFAOYSA-N 2-$l^{1}-oxidanylpropane Chemical compound CC(C)[O] ZOAMZFNAPHWBEN-UHFFFAOYSA-N 0.000 description 1
- XWFCJSXTVSOIDN-UHFFFAOYSA-N 2-propan-2-ylbutane-1,4-diol Chemical compound CC(C)C(CO)CCO XWFCJSXTVSOIDN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 239000004258 Ethoxyquin Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
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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
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
-
- 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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
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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
- C08G18/0895—Manufacture of polymers by continuous processes
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
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Abstract
一种聚碳酸酯二醇及使用该聚碳酸酯二醇制得的热塑性聚氨酯,该聚碳酸酯包括三种来自二醇的重复单元,且其中一种重复单元来自烷氧化二醇。
Description
技术领域
本发明有关于一种用于热塑性弹性体或聚氨酯的原料,更详而言,有关于一种适用于热塑性弹性体或聚氨酯的聚碳酸酯二醇。
背景技术
聚碳酸酯二醇用于制备聚氨酯或热塑性弹性体时,聚碳酸酯二醇除了作为软段,并提升耐水解性、耐光性、耐氧化劣化性及耐热性。但是,以1,6-己二醇作为原料的聚碳酸酯二醇由于具有结晶性,而导致使用此种聚碳酸酯二醇的聚氨酯存在柔软性、弹性恢复率较低的缺点。为解决该等问题,揭示有使用至少二种的二醇的脂肪族共聚碳酸酯二醇。其中,特别是使用1,4-丁二醇的脂肪族共聚碳酸酯二醇。
此外,TW I443125揭露透过调整1,4-丁二醇与1,6-己二醇等单体在聚合物中的重复单元摩尔比例,以改善聚氨酯强度、伸度、反跳弹性。
另一方面,TW I316068发现使用3-甲基-1,5-戊二醇或三甲基-1,6-己二醇作为单体以制备聚碳酸酯二醇,仍无法改善聚碳酸酯二醇系聚氨酯的耐油性,但使用2-甲基-1,3-丙二醇的特定二醇单体与一种以上二醇的脂肪族共聚碳酸酯二醇,则可提升聚氨酯的耐油性、耐水解性、耐候性。
因此,开发一种具有耐油性、耐候性及柔软性的聚碳酸酯二醇,实已成为目前亟欲解决的课题。
发明内容
本发明提供一种聚碳酸酯二醇,包括式(A)、式(B)、式(C)的重复单元及位于该聚碳酸酯二醇两末端的羟基,其中,式(A)与式(B)的摩尔比为1:99至99:1,且式(A)与式(B)的摩尔数总和与式(C)的摩尔比为1:99至99:1,
式中,R1为除了来自2-甲基-1,3-丙二醇的亚烷基外的C2-C20亚烷基;
R2为直链或具支链的C2-C20亚烷基;以及
R3为直链或具支链的C2-C10亚烷基,且m及n各自为0至10的整数,且m+n≥1。
本发明还提供一种热塑性聚氨酯,是本发明的聚碳酸酯二醇与聚异氰酸酯共聚而得。
根据本发明的聚碳酸酯二醇,可令制得的热塑性聚氨酯具有较佳的柔软度及伸长率,并具有相当的耐油性和耐候性,适合应用于纤维、涂料及粘着剂。
具体实施方式
以下通过特定的具体实施例说明本发明的实施方式,该领域技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。
本发明提供一种聚碳酸酯二醇,包括式(A)、式(B)、式(C)的重复单元及位于该聚碳酸酯二醇两末端的羟基,其中,式(A)与式(B)的摩尔比为1:99至99:1,且式(A)与式(B)的摩尔数总和与式(C)的摩尔比为1:99至99:1,
式中,R1为除了来自2-甲基-1,3-丙二醇的亚烷基外的C2-C20亚烷基;
R2为直链或具支链的C2-C20亚烷基;以及
R3为直链或具支链的C2-C10亚烷基,且m及n各自为0至10的整数,且m+n≥1。
本发明制造聚碳酸酯二醇的方法并无特别限制,可参考TW I316068所揭露的方法。
于一实施例中,将二醇与碳酸酯进行酯交换反应,以得到聚碳酸酯预聚物,接着,令该聚碳酸酯预聚物缩合而得本发明的聚碳酸酯二醇。
在首先进行的酯交换反应中,使用2-甲基-1,3-丙二醇与至少另外二种二醇单体反应,该另外二种二醇单体的一者可具有式(D)结构,
HO-R1-OH (D)
式中,R1为除了来自2-甲基-1,3-丙二醇的亚烷基外的C2-C20亚烷基。
具有式(D)结构的二醇单体的非限制性实例包括乙二醇、1,2-丙二醇、1,3-丙二醇、新戊二醇、1,4-丁二醇、2-异丙基-1,4-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、2,4-二甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、1,6-己二醇、2-乙基-1,6-己二醇、1,7-庚二醇、1,8-辛二醇、2-甲基-1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,3-环己二醇、1,4-环己二醇、1,4-环己烷二甲醇、2-双(4-羟基环己基)-丙烷等。
又,式(D)所示的二醇可单独使用或二种以上并用。其中又以使用1,4-丁二醇、1,5-戊二醇、1,6-己二醇可得具有更优良的耐油性、柔软性、耐水解性、耐候性等均衡物性的聚氨酯。在此具体实施例中,本发明的聚碳酸酯二醇中,R1为亚丁基、亚戊基或亚己基。
除了前述二醇单体外,还在反应中使用聚醚二醇的单体,以令所得的聚碳酸酯二醇具有式(C)的重复单元。
该聚醚二醇的单体可由直链或具支链的具有2至20个碳原子的二醇类化合物与具有2至10个碳原子的环氧化物反应得到,具有式(C)结构的二醇单体的非限制性实例包括二甘醇、三甘醇、乙氧基化-1,3-丙二醇、丙氧基化-1,3-丙二醇、乙氧基化-2-甲基-1,3-丙二醇、丙氧基化-2-甲基-1,3-丙二醇、乙氧基化-1,4-丁二醇、丙氧基化-1,4-丁二醇、一缩二丁二醇、二缩三丁二醇、乙氧基化-1,5-戊二醇、丙氧基化-1,5-戊二醇、乙氧基化新戊二醇、丙氧基化新戊二醇、乙氧基化-1,6-己二醇、丙氧基化-1,6-己二醇及聚四亚甲基醚二醇等。
于制造聚碳酸酯二醇的一具体实施例中,包括二个步骤,第一步骤中以二醇与碳酸酯的酯交换反应为主反应。伴随着该酯交换反应,可使含羟基的化合物由碳酸酯脱离。
第一步骤的反应温度一般为120℃至180℃,优选130℃至170℃。温度低于120℃时会减缓酯交换的反应速度,而加长反应时间,又温度超过180℃时将有明显的副反应。第一步骤所得的聚碳酸酯预聚物的聚合度一般为2至10。
第二步骤为去除未反应的原料,且同第一步骤使用精馏塔于减压下进行第二步骤。使用精馏塔时该精馏塔的分离性能是重点,理论上段数为5段以上,但以使用7段以上的精馏塔为佳。又,回流比可依所使用的精馏塔能力设定而异,一般设定为0.5至3。
第二步骤的反应温度一般为120℃至200℃,优选130℃至190℃。温度低于120℃时会减缓自己缩合的反应速度,而加长反应时间故不宜。又温度超过200℃时将无法忽视聚碳酸酯预聚物分解。
本发明为了加快酯交换反应的反应速度可使用催化剂。该催化剂如,锂、钠、钾、铷、铯、镁、钙、锶、钡、钛、锆、铪、钴、锌、铝、镍、锡、铅、锑、砷、铈等金属及其化合物。该金属化合物如,氧化物、氢氧化物、盐、烷氧化物、有机化合物等。该催化剂中又以使用四异丙氧基钛、四丁氧基钛等钛化合物、二丁基锡二月桂酸盐、二丁基锡氧化物、二丁基锡二乙酸盐等锡化合物、乙酸铅、硬脂酸铅等铅化合物为佳。为了避免降低物性,该催化剂对原料总添加重量的使用量优选为1至10000ppm,更优选为1至1000ppm。
根据前述的制法,于非限制性实施例中,该聚碳酸酯二醇中的R1为亚丁基、亚戊基或亚己基。此外,R2为直链或具支链的C2-C20亚烷基;且R3为直链或具支链的C2-C10亚烷基,m及n为0至10的整数,且m+n≥1。
于另一具体实施例中,R1为除了来自2-甲基-1,3-丙二醇的亚烷基外的C2-C20亚烷基;R2为直链或具支链的C2-C20亚烷基;且R3为亚丁基,且m为0。
于又一具体实施例中,R1为除了来自2-甲基-1,3-丙二醇的亚烷基外的C2-C20亚烷基;R2为直链或具支链的C2-C10亚烷基,R3为C2-C3亚烷基。
另外,为满足热塑性聚氨酯的性质,聚碳酸酯二醇的数均分子量至少大于等于200,且不高于10000,通常数均分子量为500至5000。
于本发明的聚碳酸酯二醇的一具体实施例中,式(A)与式(B)的摩尔比为10:90至90:10。于另一具体实施例中,式(A)与式(B)的摩尔比为20:80至80:20。
于本发明的聚碳酸酯二醇的一具体实施例中,式(A)与式(B)的摩尔数总和与式(C)的摩尔比为25:75至99:1。于另一具体实施例中,式(A)与式(B)的摩尔数总和与式(C)的摩尔比为50:50至99:1。亦即,式(A)、式(B)及式(C)的重复单元可选自前述的二醇单体和聚醚二醇的单体,使聚碳酸酯二醇中的式(A)与式(B)的摩尔数总和与式(C)的摩尔比为25:75至99:1或50:50至99:1。
在实施例和比较例中,关于所述聚碳酸酯二醇和热塑性聚氨酯的多种性质根据如下试验方式进行测试。
1.羟基值(OHV):
用50ml吡啶稀释12.5g乙酸酐制备乙酰化试剂。将2.5至5.0g样品精称至100ml茄型烧瓶后,以吸量管加入5ml乙酰化试剂及10ml甲苯,并安装冷凝管。以100℃搅拌加热1小时后,以吸量管加入2.5ml蒸馏水再加热搅拌10分钟。冷却2至3分钟后加入12.5ml乙醇,并滴入2至3滴酚酞作为指示剂,其后以0.5mol/l氢氧化钾乙醇溶液滴定。另外将5ml乙酰化试剂、10ml甲苯、2.5ml蒸馏水加入100ml茄型烧瓶中,加热搅拌10分钟后进行相同滴定(空试验),再以下列公式(i)由结果计算OH价。
OH价(mg-KOH/g)={(b-a)x28.05x f}/e(i)
a:样品滴定量(ml)
b:空试验滴定量(ml)
e:样品重量(g)
f:滴定液的因数
2.分子量:
数均分子量=2/(羟基值x10-3/56.11)
3.黏度:
将生成物加热至60℃后,使用E型粘度计(Brookfield制HADV-I+CP,转子:LV-4)进行测试。
4.玻璃转移温度(Tg):
以示差扫描量热仪(Perkin Elmer制Pyris 1)进行测试,测定温度范围-100℃至200℃。
5.机械性质:
对宽10mm、长100mm、厚0.1mm的哑铃形聚氨酯膜片,根据JIS K6301,使用万能拉力机(Cometech Testing Machines Co.,Ltd.生产的QC-506A)测定拉伸模数、拉伸断裂应力及伸长率。
6.溶胀率测试:
将厚度为0.07~0.1mm的聚氨酯薄膜浸渍于45℃油酸中1周,测定溶胀率并以其做为耐化性的指标。溶胀率(%)=((试验后重量-试验前重量)/试验前重量)X100。
7.耐候性:
将厚度为0.07~0.1mm的聚氨酯薄膜置于耐候试验机(由T-Machine TechnologyCo.,Ltd.生产的TMJ-9707A)中,于200小时测试中,重复具有包括12分钟降雨的60分钟循环,经由机械性能测试(Cometech Testing Machines Co.,Ltd.生产的QC-506A)观察拉伸断裂应力的保持率。耐候性评价:保持率≥80%标记为A,保持率介于60%至80%的间的标记为B,保持率<60%标记为C。
实施例1、聚碳酸酯二醇的制备
在具备精馏塔、搅拌机、温度计、氮导入管的玻璃圆底烧瓶中,投料906g的碳酸二甲酯(DMC)、300g的1,4-丁二醇(以下称BDO)、300g的2-甲基-1,3-丙二醇(以下称MPO)、132g的乙氧化2-甲基-1,3-丙二醇和0.1g的四丁氧基钛催化剂,在常压、通氮气流的条件下搅拌该圆底烧瓶中的投料,在将甲醇和碳酸二甲酯的混合物蒸馏除去的同时,进行酯交换反应8小时。在此过程中,反应温度自95℃缓慢地升温至150℃,期间调节馏出物的组成,使得其成为甲醇和碳酸二甲酯的共沸组成或其相近组成。
其后,缓慢地减压至100torr,在搅拌下,将甲醇和碳酸二甲酯的混合物蒸馏除去的同时,在150℃进一步进行酯交换反应1小时,接着,再进一步减压至10torr并反应5小时。反应结束后(甲醇和碳酸二甲酯的蒸馏除去结束后),将反应液冷却至室温,得到992g的聚碳酸酯二醇共聚物。
所得到的聚碳酸酯二醇共聚物的数均分子量为1955,羟基值为57.4mgKOH/g。
实施例2至8及比较例1至4的反应参照下表一所示内容进行,并将测试结果纪录于表一。
表一
a.A表示乙氧基化-2-甲基-1,3-丙二醇;B表示乙氧基化-1,6-己二醇;C表示聚四亚甲基醚二醇(分子量250)。
b.二醇表示二醇单体和聚醚二醇的单体的摩尔数总和。
热塑性聚氨酯的制备
利用在实施例1至8和比较例1至4中获得的各种聚碳酸酯二醇通过如下方法制备热塑性聚氨酯。
将预先加热至70℃的聚碳酸酯二醇0.1mol放入可分离式烧瓶,并加入0.2mol 1,4-丁二醇、1滴二月桂酸二丁基锡及600g二甲基甲酰胺(DMF)并于55℃下搅拌均匀并使各化合物溶于DMF中。其次加入0.3mol二苯基甲烷二异氰酸酯(MDI)并于80℃下反应8小时。其后,取得固成份约30%的聚氨酯DMF溶液。
将此聚氨酯溶液以刮刀涂布于聚乙烯膜上,并干燥取得热塑性聚氨酯膜。测定此膜的物性并记录于表二。
表二
根据表二的结果,可知比较例2至4中,若聚碳酸酯二醇不含式(A)与式(B)的重复单元,制得的热塑性聚氨酯的耐候性不佳,不利于后续应用。反之,本发明聚碳酸酯二醇制得的热塑性聚氨酯具有优异的耐候性,此外,相较于比较例1的热塑性聚氨酯,本发明聚碳酸酯二醇制得的热塑性聚氨酯具有较佳的柔软度及伸长率,并具有相当的耐油性和耐候性。
另一方面,相较于比较例1,本发明聚碳酸酯二醇具有较低的粘度,更可避免合成聚氨酯时发生的爬竿现象(Weissenberg effect),减少添加的溶剂,改善产物的流动性,易于涂布于基材。若应用于水性聚氨酯分散体(Polyurethane Dispersion)预聚合制程,将有利于水分散的情况。
上述实施例仅例示说明本发明的原理及其功效,而非用于限制本发明。任何该领域技术人员均可在不违背本发明的精神及范畴下,对上述实施例进行修饰与改变。因此,本发明的权利保护范围,应如权利要求书所列,在不影响本发明所能产生的功效及所能达成的目的下,均应仍落在本发明揭示的技术内容所能涵盖的范围内。
Claims (6)
1.一种聚碳酸酯二醇,包括式(A)、式(B)、式(C)的重复单元及位于该聚碳酸酯二醇两末端的羟基,其中,式(A)与式(B)的摩尔比为20:80至80:20,且式(A)与式(B)的摩尔数总和与式(C)的摩尔比为50:50至99:1,
式中,R1为除了来自2-甲基-1,3-丙二醇的亚烷基外的C2-C20亚烷基;
R2为直链或具有支链的C2-C20亚烷基;以及
R3为直链或具有支链的C2-C10亚烷基,且m及n各自为0至10的整数,且m+n≥1。
2.如权利要求1所述的聚碳酸酯二醇,其特征在于,R1为亚丁基、亚戊基或亚己基。
3.如权利要求1所述的聚碳酸酯二醇,其特征在于,R3为亚丁基,且m为0。
4.如权利要求1所述的聚碳酸酯二醇,其特征在于,R2为直链或具有支链的C2-C10亚烷基,R3为C2-C3亚烷基。
5.如权利要求1所述的聚碳酸酯二醇,其数均分子量为200至10000。
6.一种热塑性聚氨酯,是权利要求1所述的聚碳酸酯二醇与聚异氰酸酯共聚而得。
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