CN117597377A - 聚酯多元醇及其制备方法 - Google Patents
聚酯多元醇及其制备方法 Download PDFInfo
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- CN117597377A CN117597377A CN202280047644.9A CN202280047644A CN117597377A CN 117597377 A CN117597377 A CN 117597377A CN 202280047644 A CN202280047644 A CN 202280047644A CN 117597377 A CN117597377 A CN 117597377A
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- Prior art keywords
- acid
- polyester polyol
- reaction mixture
- anhydrohexitol
- polyol according
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 41
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- 239000000853 adhesive Substances 0.000 claims abstract description 25
- 239000011541 reaction mixture Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 150000007513 acids Chemical class 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims description 38
- 150000003077 polyols Chemical class 0.000 claims description 35
- 239000012948 isocyanate Substances 0.000 claims description 24
- 150000002513 isocyanates Chemical class 0.000 claims description 24
- -1 aliphatic polyol Chemical class 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 19
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000539 dimer Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
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- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 57
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 150000003606 tin compounds Chemical class 0.000 description 5
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 4
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明涉及衍生自反应混合物的聚酯多元醇,所述反应混合物包含至少一种失水己糖醇、至少一种多官能羧酸和至少一种非金属无机酸性催化剂,所述非金属无机酸性催化剂选自具有呈+1氧化态的磷原子的非金属无机酸性化合物、具有呈+3氧化态的磷原子的非金属无机酸性化合物、及其混合物。此外,本发明涉及所述聚酯多元醇的制备方法及其在聚氨酯粘合剂组合物中的用途。
Description
技术领域
本发明涉及聚酯多元醇、特别是生物基(bio-based)聚酯多元醇,及其制备方法。此外,本发明涉及包含所述聚酯多元醇的聚氨酯粘合剂组合物。
背景技术
聚酯多元醇是用于生产聚氨酯的原料之一,并且通常是由多官能羧酸与多元醇的缩聚获得的线性聚合物。缩聚是可逆反应,但是当反应混合物的粘度在反应的后期阶段增加时,作为反应产物的水无法容易地从反应混合物中分离。因此,必须通过加热、增加搅拌速率等来维持正反应方向。然而,如果反应时间过长,则成本会增加,并且聚酯多元醇的性质会劣化。为了缩短反应时间,聚酯多元醇的缩聚中的合适催化剂已经被广泛使用。
另一方面,已经成功开发可再生且生物基衍生的资源,并且一系列生物基衍生的多元醇(如椰子油、天然橡胶、橡胶籽油、腰果仁/壳油、大豆油、以及异山梨醇)已经用于聚酯多元醇。
其中异山梨醇可以通过山梨糖醇的催化脱水来产生,山梨糖醇是广泛的生物可再生葡萄糖的氢化产物。作为典型的生物基化学品,异山梨醇具有许多独特的特性(如V形二醇分子的刚性结构、高热稳定性、可生物降解性、可再生性、水溶性和无毒性),其可以向具有异山梨醇作为单体的聚合物材料贡献许多特征。近来,已经将异山梨醇用于制备用于聚氨酯粘合剂的聚酯多元醇。
例如,US20130109804 A1公开了一种通过使用金属催化剂作为酯交换催化剂使以下物质反应而获得的聚碳酸酯二醇:至少一种选自异山梨醇、异二缩甘露醇(isomannide)和异二缩艾杜糖醇(isoidide)的二醇;可以含有杂原子的具有1-15个碳的二醇;以及(iii)碳酸二酯。
US 9309438 B2公开了一种可辐射固化的组合物,所述组合物包含:至少一种(甲基)丙烯酸酯化的化合物(A);以及至少一种惰性OH封端的聚酯(B),其是通过使用强酸(如烷基磺酸和/或芳基磺酸)或有机金属化合物作为催化剂由包含至少一种环醚多元醇的多元醇组分和多元酸组分而制备的。
US20090253888 A1公开了一种通过使用有机次膦酸化合物作为催化剂与金属催化剂组合来制备聚酯的方法。
然而,由于异山梨醇的反应性,当通过常规方法聚合含有高含量异山梨醇结构单元的聚酯多元醇时,已经发现反应产物呈现深色,从而表明异山梨醇在聚合期间在常规催化剂的存在下遇到副作用。因此,期望通过使用具有成本效益的催化剂以高转化率生产含有高异山梨醇含量的聚酯多元醇。
发明内容
本发明的第一目的是提供衍生自反应混合物的聚酯多元醇,所述反应混合物包含:
至少一种失水己糖醇,
至少一种多官能羧酸,以及
至少一种非金属无机酸性催化剂,所述非金属无机酸性催化剂选自具有呈+1氧化态的磷原子的非金属无机酸性化合物、具有呈+3氧化态的磷原子的非金属无机酸性化合物、及其混合物。
本发明的另一目的是提供包含多元醇组分和异氰酸酯组分的聚氨酯粘合剂组合物,所述多元醇组分包含至少一种根据本发明的聚酯多元醇,所述异氰酸酯组分包含至少一种多官能异氰酸酯。
本发明的又一目的是提供包含预聚物的聚氨酯粘合剂组合物,所述预聚物是多元醇组分与异氰酸酯组分的反应产物,所述多元醇组分包含至少一种根据本发明的聚酯多元醇,所述异氰酸酯组分包含至少一种多官能异氰酸酯。
本发明的又一目的是提供包含根据本发明的反应性粘合剂组合物的单部分、两部分或多部分粘合剂体系。
本发明的又一目的是提供将材料粘合在一起的方法,所述方法包括施加根据本发明的单部分、两部分或多部分粘合剂体系。
具体实施方式
本发明在以下段落中被更详细地描述。除非明确指示相反,否则如此描述的每个方面可以与任何其他一个或多个方面相结合。特别地,被指出为优选或有利的任何特征可以与被指出为优选或有利的任何其他一个或多个特征相结合。
除非另有定义,否则在公开本发明中使用的所有术语(包括技术术语和科学术语)具有如本发明所属领域的普通技术人员通常所理解的含义。通过进一步指导,术语定义被包括以更好地理解本发明的教导。
如本文中所用,除非上下文另外明确指出,否则单数形式“一个/一种(a/an)”和“所述/该(the)”包括单数指称对象和复数指称对象两者。
如本文中所用,术语“包含(comprising/comprises/comprised of)”与“包括(including/includes)”或“含有(containing/contains)”同义,并且是包括性的或开放式的,并且不排除附加的未被叙述的成员、要素或方法步骤。
术语“生物基”是指至少部分来源于生物质(如植物、树木或动物)的材料或产物,其可以已经经历物理处理、化学处理或生物处理。术语“完全生物基”是指完全来源于生物质(如植物、树木或动物)的材料或产物,其可以已经经历物理处理、化学处理或生物处理。
对数字端点的叙述包括各个范围内包含的所有数字和分数、以及所叙述的端点。
本说明书中引用的所有参考文献均特此通过引用整体并入。
除非另外说明,否则如果在本文中提及聚合物的分子量,则该提及是指数均重量Mn。聚合物的数均分子量Mn可以例如通过凝胶渗透色谱(GPC)用THF作为洗脱剂来测定。如果没有另外说明,则所有给定的分子量都是通过使用聚苯乙烯标准物校准的GPC测定的那些。平均分子量Mw也可以通过GPC测定,如针对Mn所述的。
所公开的聚酯多元醇衍生自/获自反应混合物,所述反应混合物包含至少一种失水己糖醇、至少一种多官能羧酸和至少一种非金属无机酸性催化剂,所述非金属无机酸性催化剂选自具有呈+1氧化态的磷原子的非金属无机酸性化合物、具有呈+3氧化态的磷原子的非金属无机酸性化合物、及其混合物。
失水己糖醇是通过己糖醇(如山梨糖醇(葡萄糖醇)、甘露糖醇、艾杜糖醇)的脱水而获得的,所述己糖醇是通过使通常来源于一些生物原料(如小麦、玉米、纤维素)的己糖(如葡萄糖、甘露糖、艾杜糖)的羰基还原而产生的。
双重脱水产生二失水己糖醇。通常,失水己糖醇是二失水己糖醇,如二失水甘露糖醇、二失水山梨糖醇、二失水艾杜糖醇、及其混合物。二失水己糖醇优选为二失水山梨糖醇,如异山梨醇、异二缩甘露醇和异二缩艾杜糖醇,并且更特别为异山梨醇。一些公司已经专门从事异山梨醇、异二缩甘露醇和异二缩艾杜糖醇的生产。
优选地,基于聚酯多元醇的反应物的总摩尔数,至少一种失水己糖醇的量为20摩尔%至60摩尔%。
除失水己糖醇以外,聚酯多元醇的反应物可以任选地包含至少一种除失水己糖醇以外的多元醇,以与多官能羧酸反应。
此类多元醇的实例包括一乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇(包括R-形式、S-形式和外消旋体)、1,4-丁二醇、1,4-戊二醇、3-甲基戊烷-1,5-二醇、新戊二醇(2,2-二甲基-1,3-丙二醇)、1,5-戊二醇、1,6-己二醇、1,8-辛二醇(1,8-otaneglycol)、环己烷二甲醇、2-甲基丙烷-1,3-二醇、二乙二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、聚丙二醇、聚丙二醇、二丁二醇和聚丁二醇。
优选地,除失水己糖醇以外的多元醇是完全生物基的。此类多元醇的实例包括但不限于甘油、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇(包括R-形式、S-形式和外消旋体)、1,4-丁二醇、1,4-戊二醇、1,5-戊二醇、乙二醇、二乙二醇和三乙二醇。这些多元醇被单独使用或组合使用。
在一个实施方案中,聚酯多元醇的反应物包含至少一种除失水己糖醇以外的多元醇。如果存在,则基于聚酯多元醇的反应物的总摩尔数,除失水己糖醇以外的多元醇的量为1摩尔%至35摩尔%。
在另一个实施方案中,聚酯多元醇的反应物仅包含失水己糖醇作为用于制备根据本发明的聚酯多元醇的多元醇来源。
聚酯多元醇是可通过在根据本发明的催化剂的存在下使失水己糖醇和任选存在的至少一种除失水己糖醇以外的多元醇与亚化学计算量的多官能羧酸缩聚来制备的。优选地,多官能羧酸具有2-36个碳原子,如二羧酸和/或三羧酸、或其反应性衍生物(如羧酸酐、羧酸氯和羧酸酯)。
二羧酸的实例包括己二酸、琥珀酸、壬二酸、癸二酸、十二烷二酸、十四烷二酸、十六烷二酸、十八烷二酸、衣康酸、呋喃二羧酸、间苯二甲酸、对苯二甲酸、邻苯二甲酸、二聚脂肪酸、三聚脂肪酸等。这些二羧酸被单独使用或组合使用。羧酸酐的实例包括己二酸酐、琥珀酸酐等。这些二羧酸酐被单独使用或组合使用。在一个实施方案中,多官能羧酸选自琥珀酸、壬二酸、癸二酸、二聚脂肪酸、三聚脂肪酸、及其混合物。
二聚脂肪酸是单不饱和酸或多不饱和酸和/或其酯的二聚产物。优选的二聚脂肪酸是C10-至C36-、更优选地C12-至C24-、特别是C14-至C22-烷基链的二聚物。合适的二聚脂肪酸包括油酸、亚油酸、亚麻酸、棕榈油酸和反油酸的二聚产物。也可以使用在天然脂肪和油类(例如,向日葵油、大豆油、橄榄油、菜籽油、棉籽油和妥尔油)的水解中获得的不饱和脂肪酸混合物的二聚产物。二聚(二聚物)脂肪酸的实例是可商购自Croda的Pripol 1019、1013、1017、1006。
根据本发明,基于聚酯多元醇的反应物的总摩尔数,至少一种多官能羧酸的量不大于50摩尔%,并且优选为40摩尔%至50摩尔%。
失水己糖醇和任选存在的多元醇与多官能羧酸的缩聚在至少一种催化剂的存在下进行。催化剂是非金属无机酸性催化剂,所述非金属无机酸性催化剂选自具有呈+1氧化态的磷原子的非金属无机酸性化合物、具有呈+3氧化态的磷原子的非金属无机酸性化合物、及其混合物。在一个优选实施方案中,至少一种非金属无机酸性催化剂选自次膦酸、膦酸、及其混合物。在一个更优选的实施方案中,非金属无机酸性催化剂是次膦酸。
用于制备聚酯多元醇的反应混合物还可以包含至少一种溶剂(如水)。如果存在,则溶剂的含量为反应物的总重量的0.01-1重量%、更特别是0.1-0.5重量%。非金属无机酸性催化剂可以首先以5∶1至1∶5、优选地1∶1的重量比溶解于水中,并且然后与其他反应物混合以形成反应混合物。
本发明人已经出乎意料地发现,根据本发明的非金属无机酸性催化剂可以防止在升高的温度下的缩聚反应期间(例如,在聚合反应器的局部区域处)失水己糖醇的降解,并且相较于相当昂贵的常规使用的催化剂(如金属催化剂和有机磷酸),可以减少此类聚酯多元醇的大规模生产的成本。此外,通过使用根据本发明的非金属无机酸性催化剂,基于失水己糖醇的聚酯多元醇的制造不产生不符合化学品登记和法规的有害副产物。因此,可以克服在利用有机磷化合物生产含有高异山梨醇含量的聚酯多元醇中的成本和技术挑战(如期望的产物规格、浅的产物颜色、较短的反应时间、以及较少的副反应)。
优选地,缩聚反应中使用的非金属无机酸性催化剂的量的范围为反应物的总重量的0.001-5重量%、更特别是0.02-1重量%。
此外,聚酯多元醇的反应混合物基本上不包含其他催化剂,如有机磷酸、金属催化剂、胺催化剂、或具有呈+5氧化态的磷原子的无机磷酸。优选地,基于反应混合物的总重量,其包含少于0.05重量%、特别是少于0.02重量%的此类催化剂。在一个优选实施方案中,聚酯多元醇的反应混合物不含其他催化剂。
金属催化剂的实例是铝醇盐、钛醇盐、镁醇盐和锆醇盐、锡化合物,更特别是有机锡羧酸盐(如二月桂酸二丁基锡、二乙酸二丁基锡、双-(2-乙基己酸)二丁基锡)或其他有机锡化合物(如二丁基氧化锡、二丁基二甲氧基锡、二丁基二溴化锡、二丁基二氯化锡、二叔丁基二氯化锡、二甲基二溴化锡、二甲基二氯化锡、二苯基二氯化锡或辛酸锡)、乙酸铁、苯甲酸铁、环烷酸铁;乙酰丙酮铁、乙酸锰、环烷酸锰和乙酰丙酮锰。
根据本发明,含有较高量的失水己糖醇结构单元的聚酯多元醇优选通过包含以下步骤的方法来制备:(1)提供包含至少一种失水己糖醇、至少一种多官能羧酸、至少一种非金属无机酸性催化剂和任选存在的至少一种线性或支化脂族多元醇的反应混合物,以形成混合物;(2)将混合物逐步加热到200℃至220℃,并且在氮气流下保持20-40小时;(3)将压力逐步降低到1-300mbar以完成反应;以及(4)当反应混合物的酸值不超过5时冷却反应混合物,并且获得聚酯多元醇。
在本发明中,对通过如上文所述的方法制备的聚酯多元醇的物理性质没有限制。优选地,聚酯多元醇是完全生物基的,并且在室温下呈无定形液体、结晶固体或无定形固体形式。
通常,对粘合剂组合物中使用的聚酯多元醇的分子量没有限制,只要其对粘合剂组合物和已固化粘合剂的性质没有负面影响即可。优选地,聚酯多元醇的分子量Mn为500-20000g/mol、特别是1000-10000g/mol。
在本发明中,聚酯多元醇的酸值优选为0.1-5mg KOH/g、优选地1-3mg KOH/g。假设所有包含在1g树脂中的酸基团均为游离酸,根据本发明的聚酯多元醇的“酸值”通过中和该酸所需的氢氧化钾的毫克数的计算值来表示。因此,即使酸基团以碱形式存在于实际体系中,仍假定其为游离酸。根据本发明的“酸值”是根据DIN 51558通过如下方法来测定的:将聚酯多元醇溶解于溶剂中,添加酚酞作为指示剂,并且用0.1mol/l氢氧化钾-乙醇溶液滴定。
在本发明中,聚酯多元醇的羟值可以为5-150mg KOH/g、优选地10-120mg KOH/g、特别是15-100mg KOH/g。如本文中所用,羟值意指当1g树脂被乙酰化时,中和与羟基键合的乙酸所需的氢氧化钾的毫克数。
根据本发明的“羟值”是根据DIN 51558通过如下方法来测定的:将乙酰化试剂添加至聚酯多元醇,用甘油溶液加热,使其冷却,然后添加酚酞作为指示剂,并且用氢氧化钾-乙醇溶液滴定。
在本发明中,聚酯多元醇的玻璃化转变温度可以为-100℃至100℃。聚酯多元醇的玻璃化转变温度是使用差示扫描量热计来测量的。对于适当量的样品,通过差示扫描量热法以10℃/分钟的升温速率测量DSC曲线,并且将所获得的DSC曲线的拐点的温度视为玻璃化转变温度。
在一个实施方案中,聚酯多元醇、优选地完全生物基衍生的聚酯多元醇是无定形液体。优选地,此类聚酯多元醇的酸值为0.1-3mg KOH/g。优选地,此类聚酯多元醇的羟值为30-120mg KOH/g、更优选地50-100mg KOH/g。优选地,此类聚酯多元醇的Tg为-70℃至-20℃、更优选地-30℃至-60℃。
在另一个实施方案中,聚酯多元醇、优选地完全生物基衍生的聚酯多元醇是结晶固体。优选地,此类聚酯多元醇的酸值为0.1-3mg KOH/g。优选地,此类聚酯多元醇的羟值为20-100mg KOH/g、更优选地30-60mg KOH/g。优选地,此类聚酯多元醇的熔融温度为30-100℃、优选地40-70℃。
在又一个实施方案中,聚酯多元醇、优选地完全生物衍生的聚酯多元醇是无定形固体。优选地,此类聚酯多元醇的酸值为0.1-3mg KOH/g。优选地,此类聚酯多元醇的羟值为20-100mg KOH/g、更优选地30-80mg KOH/g。优选地,此类聚酯多元醇的Tg为-15℃至80℃、更优选地-10℃至60℃。
本发明的另一目的是提供包含多元醇组分和异氰酸酯组分的反应性粘合剂组合物,所述多元醇组分包含至少一种根据本发明的聚酯多元醇,所述异氰酸酯组分包含至少一种多官能异氰酸酯。
根据本发明,基于反应性粘合剂组合物的总重量,反应性粘合剂组合物包含量为5重量%至80重量%、优选地10重量%至50重量%的聚酯多元醇。
本发明的又一目的提供包含预聚物的聚氨酯粘合剂组合物,所述预聚物是由包含多元醇组分和异氰酸酯组分的反应混合物获得的反应产物,所述多元醇组分包含至少一种根据本发明的聚酯多元醇,所述异氰酸酯组分包含至少一种多官能异氰酸酯。
根据本发明,基于反应物的总重量,预聚物的反应物包含量为5重量%至80重量%、优选地10重量%至50重量%的聚酯多元醇。
可以用于实施本发明的多官能异氰酸酯包括亚烷基二异氰酸酯、亚环烷基二异氰酸酯、芳族二异氰酸酯和脂族-芳族二异氰酸酯。合适的含异氰酸酯的化合物的具体实例包括但不限于:亚乙基二异氰酸酯(ethylene diisocyanate)、亚乙基二异氰酸酯(ethylidene diisocyanate)、亚丙基二异氰酸酯、亚丁基二异氰酸酯、三亚甲基二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、亚环戊基-1,3-二异氰酸酯、亚环己基-1,4-二异氰酸酯、亚环己基-1,2-二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、2,2-二苯基丙烷-4,4’-二异氰酸酯、亚二甲苯基二异氰酸酯、1,4-亚萘基二异氰酸酯、1,5-亚萘基二异氰酸酯、间亚苯基二异氰酸酯、对亚苯基二异氰酸酯、二苯基-4,4’-二异氰酸酯、偶氮苯-4,4’-二异氰酸酯、二苯基砜-4,4’-二异氰酸酯、2,4-甲代亚苯基二异氰酸酯、二氯六亚甲基二异氰酸酯、亚糠基二异氰酸酯、1-氯苯-2,4-二异氰酸酯、4,4’,4”-三异氰酸基三苯基甲烷、1,3,5-三异氰酸基苯、2,4,6-三异氰酸基甲苯、4,4’-二甲基二苯基甲烷-2,2’,5,5-四异氰酸酯等。虽然此类化合物是可商购获得的,但用于合成此类化合物的方法是本领域公知的。也可以在本发明中使用上述单体异氰酸酯的低聚物(如二聚物或三聚物)。优选地,多官能异氰酸酯是4,4’-二苯基甲烷二异氰酸酯(MDI)。
多官能异氰酸酯也包括封端的多异氰酸酯,如单醇(mono-ol)或单羟基酚类化合物与有机多异氰酸酯的反应产物。这包括如下有机化合物:其含有至少两个异氰酸基,并且包括烃二异氰酸酯(hydrocarbon diisocyanate)(例如,亚烷基二异氰酸酯和亚芳基二异氰酸酯)、以及已知的三异氰酸酯和聚亚甲基聚(亚苯基异氰酸酯)。
用于制备封端的异氰酸酯的说明性多异氰酸酯是:2,4’-二异氰酸基甲苯、2,6-二异氰酸基甲苯、亚甲基双(4-环己基异氰酸酯)、1,2-二异氰酸基乙烷、1,3-二异氰酸基丙烷、1,2-二异氰酸基丙烷、1,4-二异氰酸基丁烷、1,5-二异氰酸基戊烷、1,6-二异氰酸基己烷、双(3-异氰酸基丙基)醚、双(3-异氰酸基丙基)硫醚、1,7-二异氰酸基庚烷、1,5-二异氰酸基-2,2-二甲基戊烷、1,6-二异氰酸基-3-甲氧基己烷、1,8-二异氰酸基辛烷、1,5-二异氰酸基-2,2,4-三甲基戊烷、1,9-二异氰酸基壬烷、1,4-丁二醇的1,10-二异氰酸基丙基)醚、1,11-二异氰酸基十一烷、1,12-二异氰酸基十二烷、双(异氰酸基己基)硫醚、1,4-二异氰酸基苯、2,4-二异氰酸基甲代亚苯基(2,4-diisocyanatotolylene)、2,6-二异氰酸基甲代亚苯基(2,6-diisocyanatotolylene)、1,3-二异氰酸基邻二甲苯、1,3-二异氰酸基间二甲苯、1,3-二异氰酸基对二甲苯、2,4-二异氰酸基-1-氯苯、2,4-二异氰酸基-1-硝基苯、2,5-二异氰酸基-1-硝基苯、4,4-二苯基亚甲基二异氰酸酯、3,3-二苯基-亚甲基二异氰酸酯、聚亚甲基聚(亚苯基异氰酸酯)、异佛尔酮二异氰酸酯、及其混合物。
根据本发明,基于反应性粘合剂组合物或反应物的总重量,反应性粘合剂组合物或预聚物的反应物包含量为5重量%至50重量%、优选地10重量%至30重量%的多官能异氰酸酯。
反应性粘合剂组合物的多元醇组分或预聚物的反应物可以包含其他聚合物多元醇,以进一步改善粘合剂的性质。此类其他聚合物多元醇可以是生物基衍生的或基于化石的。优选地,此类聚合物多元醇也是生物基衍生的,以便增加粘合剂组合物中生物质的含量。在一个优选实施方案中,多元醇组分还包含其他生物基聚合物多元醇。在另一个优选实施方案中,基于反应性粘合剂组合物的总重量,完全生物基衍生的聚酯多元醇和其他生物基聚合物多元醇(如果存在)的量为50重量%至85重量%。
如果存在,则基于粘合剂组合物的总重量,其他聚合物多元醇以1-50重量%的量存在于粘合剂组合物中。
在优选实施方案中,至少一种多官能异氰酸酯与至少一种根据本发明的聚酯多元醇和其他聚合物多元醇(如果存在)的摩尔比(表示为NCO/OH)为5∶1至1∶1、优选地2.5∶1至1.05∶1。
催化剂可以包含在反应性粘合剂组合物中。在双组分粘合剂组合物的情况下,其可以被包含在异氰酸酯组分或多元醇组分中。当使用催化剂时,促进羟基与多官能异氰酸酯的异氰酸酯基之间的交联反应。催化剂的实例包括叔胺化合物和有机金属化合物。
叔胺化合物的实例包括三乙胺、三亚乙基二胺、N,N-二甲基苄胺、N-甲基吗啉、二氮杂双环十一烯(也称为DBU)等。
有机金属化合物的实例包括锡化合物和非锡化合物。
锡化合物的实例包括二丁基二氯化锡、二丁基氧化锡、二丁基二溴化锡、二马来酸二丁基锡、二月桂酸二丁基锡(也称为DBTDL)、二乙酸二丁基锡、二丁基硫化锡、三丁基硫化锡、三丁基氧化锡。实例包括乙酸三丁基锡、三乙基乙氧基锡、三丁基乙氧基锡、二辛基氧化锡、三丁基氯化锡、三氯乙酸三丁基锡和2-乙基己酸锡。
非锡化合物的实例包括钛化合物,如二丁基二氯化钛、钛酸四丁酯和丁氧基三氯化钛;铅化合物,如油酸铅、2-乙基己酸铅、苯甲酸铅和环烷酸铅;铁化合物,如乙基己酸铁和2,4-戊二酮酸铁(iron 2,4-pentadionate);钴化合物,如苯甲酸钴和2-乙基己酸钴;锌化合物,如环烷酸锌和2-乙基己酸锌;以及环烷酸锆。
在这些之中,从反应性和卫生方面而言,二氮杂双环十一烯(DBU)、二月桂酸二丁基锡(DBTDL)、2-乙基己酸锌等是优选的。
粘合剂组合物的催化剂可以单独使用或者以两种或更多种的组合使用。
根据本发明的粘合剂组合物可以包含或不包含有机溶剂。有机溶剂的实例将包括:杂环、脂族或芳族烃类,如甲苯、异佛尔酮、二甲苯;一元醇或多元醇,如乙基己醇、丁氧基丙醇、异丙醇、二乙二醇丁醚、甲醇、乙醇、丙醇和丁醇;醚类,如二乙二醇二甲醚和二丙二醇甲醚;乙二醇和丁二醇;酯类,如乙酸乙酯、乙酸丁酯、乙酸戊酯或乙氧基丙酸乙酯;酮类,如环己酮、甲基乙基酮(MEK)、甲基戊基酮、甲基异丁基酮(MIBK)和丙酮;以及酰胺类,如N-甲基吡咯烷酮、N-乙基吡咯烷酮、甲氧基乙酸丙酯和二甲基甲酰胺。
虽然反应性粘合剂组合物可以如上文所述直接使用,但是如果需要,则本发明的粘合剂组合物也可以同与该组合物相容的常规添加剂一起配制。添加剂可以被包含在多元醇组分和/或异氰酸酯组分中,只要其对其他成分(如多元醇和/或异氰酸酯)呈惰性即可。此类添加剂包括粘合促进剂、消泡剂、光学增白剂、分散剂、颜料、粘度改进剂、及其混合物。
将在根据本发明的粘合剂组合物中使用的合适粘合促进剂是例如硅烷化合物,如巯基丙基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷、和3-丙烯酰氧基丙基三甲氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷、双-(γ-三甲氧基甲硅烷基丙基)胺、N-β-(氨基乙基)-γ氨基丙基甲基二甲氧基硅烷、三-(γ-三甲氧基甲硅烷基)异氰脲酸酯、及其混合物。
将用作添加剂的合适消泡剂是例如丙烯酸酯共聚物。
将用作添加剂的合适光学增白剂是例如2,5-噻吩二基双(5-叔丁基-1,3-苯并噁唑)。
将使用的合适分散剂是例如高分子量烷氨基酰胺、羟基官能的羧酸酯和结构化的丙烯酸酯共聚物(structured acrylate copolymer)。
将使用的合适颜料是例如颜料膏和色浆。
将使用的合适粘度改进剂是例如气相二氧化硅。
本发明的粘合剂组合物/体系可以通过混合组分/部分/预聚物和任选存在的添加剂来产生。对混合方法没有特别限制,只要可以获得本发明的目标粘合剂即可。对混合组分的顺序也没有特别限制。根据本发明的粘合剂组合物/体系可以被产生,而无需特殊混合方法和特殊混合顺序。
本发明还提供用于将物品粘合在一起的方法,所述方法包括:将呈液体形式的本发明的粘合剂体系施加至第一物品;使第二物品与施加至第一物品的体系接触;以及使施加的体系经历将使该体系固化并且使基材粘合的条件。组合物通常以其液体或固体形式分配和储存,并且在没有水分的情况下储存。还提供包含根据本发明的粘合剂组合物的固化产物的制品。
将通过以下实施例更详细地说明本发明,所述实施例不应当被理解为限制本发明的构思。
实施例
在实施例中使用以下材料。
癸二酸获自Sigma Aldrich。
琥珀酸获自Sigma Aldrich。
异山梨醇以商品名称Polysorb PA获自Roquette。
1,3-丁二醇获自Godavari Biorefineries。
1,2-丙二醇获自Sigma Aldrich。
乙二醇获自Sigma Aldrich。
二聚物脂肪酸以商品名称Pripol获自Croda。
次膦酸获自Sigma Aldrich。
正磷酸获自Sigma Aldrich。
(2-甲氧基苯基)苯基次膦酸获自Sigma Aldrich。
异丙醇钛(IV)获自Sigma Aldrich。
2,4’-MDI获自Covestro。
聚酯多元醇的制备
根据表1中的配方制备聚酯多元醇的本发明实施例(Ex.1至Ex.6)。根据表2中的配方制备聚酯多元醇的对比例(CEx.1至CEx.5)。
用一种或多种多元酸和一种或多种多元醇装填配备有氮气喷布管、热电偶、顶置式搅拌器和蒸馏臂(distillation arm)的1升或5升4颈烧瓶。将混合物在氮气流下逐步加热到最高220℃。取决于反应组合物(单体和催化剂),完全反应花费大约20小时至40小时。从缩聚反应开始或者在缩聚反应过程期间直接添加1∶1重量比的催化剂水溶液。随后,将系统的压力逐步降低到10-300mbar,以实现完全转化。一旦酸值达到5mg KOH/g或更小的值,就冷却反应。聚酯多元醇被通过其酸值(以mg KOH/g为单位)、羟值(以mg KOH/g为单位)、在特定温度下的粘度(以Pa·s为单位)、以及根据GPC方法的Mn(以g/mol为单位)来表征。进行DSC测量,以测定最终聚酯多元醇的Tg和熔点Tm(以℃为单位)。
表1.本发明的聚酯多元醇的反应物和性质
1AS:无定形固体;2CS:结晶固体;3AL:无定形液体
表2.非根据本发明的聚酯多元醇的反应物和性质
1AS:无定形固体;2CS:结晶固体;3AL:无定形液体
如从表1和表2可以看出的,所制备的根据本发明的聚酯多元醇表现出无色至淡黄色或微黄色的颜色,而所制备的非根据本发明的聚酯多元醇表现出深色或甚至黑色,从而表明聚合过程中发生的异山梨醇的降解。此外,对比例5中聚酯多元醇的制备需要26小时(包括在真空条件下16小时),而实施例1中聚酯多元醇的制备仅需要21小时(包括在真空条件下13.5小时)。
Claims (15)
1.衍生自反应混合物的聚酯多元醇,所述反应混合物包含:
至少一种失水己糖醇,
至少一种多官能羧酸,以及
至少一种非金属无机酸性催化剂,所述非金属无机酸性催化剂选自具有呈+1氧化态的磷原子的非金属无机酸性化合物、具有呈+3氧化态的磷原子的非金属无机酸性化合物、及其混合物。
2.根据权利要求1所述的聚酯多元醇,其中所述失水己糖醇是异山梨醇。
3.根据权利要求1或2所述的聚酯多元醇,其中所述多官能羧酸是生物基的,并且优选地选自己二酸、琥珀酸、壬二酸、癸二酸、十二烷二酸、十四烷二酸、十六烷二酸、十八烷二酸、衣康酸、呋喃二羧酸、间苯二甲酸、对苯二甲酸、邻苯二甲酸、二聚脂肪酸、三聚脂肪酸、及其混合物。
4.根据权利要求1-3中任一项所述的聚酯多元醇,其中所述至少一种非金属无机酸性催化剂选自次膦酸、膦酸、及其混合物。
5.根据权利要求1-4中任一项所述的聚酯多元醇,其中,基于反应物的总摩尔数,所述至少一种失水己糖醇的量为20摩尔%至60摩尔%。
6.根据权利要求1-5中任一项所述的聚酯多元醇,其中,基于反应物的总摩尔数,所述至少一种多官能羧酸的量不大于60摩尔%、优选为20摩尔%至50摩尔%。
7.根据权利要求1-6中任一项所述的聚酯多元醇,其中所述反应混合物还包含至少一种除失水己糖醇以外的多元醇,所述多元醇优选为生物基的,并且更优选地选自甘油、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,4-戊二醇、1,5-戊二醇、乙二醇、二乙二醇、三乙二醇、及其混合物。
8.根据权利要求7所述的聚酯多元醇,其中,基于反应物的总摩尔数,所述至少一种除失水己糖醇以外的多元醇的量为1摩尔%至50摩尔%、优选地10摩尔%至40摩尔%。
9.根据权利要求1-8中任一项所述的聚酯多元醇,其中所述聚酯多元醇是液态无定形的、固态结晶的或固态无定形的。
10.根据权利要求1-9中任一项所述的聚酯多元醇,其中所述反应混合物基本上不包含金属催化剂,优选地包含基于所述反应混合物的总重量计少于0.02重量%的金属催化剂。
11.根据权利要求1-9中任一项所述的聚酯多元醇,包含量为按聚酯多元醇的重量计小于0.002%、优选地小于0.001%的金属元素。
12.制备根据权利要求1-11中任一项所述的聚酯多元醇的方法,所述方法包括以下步骤:
1)提供反应混合物,所述反应混合物包含至少一种失水己糖醇、至少一种多官能羧酸、至少一种非金属无机酸性催化剂和任选存在的至少一种线性或支化脂族多元醇,
2)将所述反应混合物逐步加热到200℃至220℃,并且在氮气流下保持20-40小时,
3)将压力逐步降低到1-300mbar,以完成反应并且获得反应产物,以及
4)当所述反应产物的酸值不超过5时冷却所述反应产物,并且获得聚酯多元醇。
13.包含多元醇组分和异氰酸酯组分的聚氨酯粘合剂组合物,所述多元醇组分包含至少一种根据权利要求1-10中任一项所述的聚酯多元醇,所述异氰酸酯组分包含至少一种多官能异氰酸酯。
14.包含预聚物的聚氨酯粘合剂组合物,所述预聚物是由包含多元醇组分和异氰酸酯组分的反应混合物获得的反应产物,所述多元醇组分包含至少一种根据本发明的聚酯多元醇,所述异氰酸酯组分包含至少一种多官能异氰酸酯。
15.制品,所述制品包含根据权利要求13或14所述的聚氨酯粘合剂组合物的固化产物。
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