CN1329625A - 用丙二酸酯和三唑混合封闭的、含甲醛的1,6－二异氰酸根络环己烷三聚体的稳定化方法 - Google Patents

用丙二酸酯和三唑混合封闭的、含甲醛的1,6－二异氰酸根络环己烷三聚体的稳定化方法 Download PDF

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CN1329625A
CN1329625A CN99814172A CN99814172A CN1329625A CN 1329625 A CN1329625 A CN 1329625A CN 99814172 A CN99814172 A CN 99814172A CN 99814172 A CN99814172 A CN 99814172A CN 1329625 A CN1329625 A CN 1329625A
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formaldehyde
triazole
ester
blocked polyisocyanate
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E·柯尼希
H·－U·梅尔－韦斯特许斯
T·克林马施
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Abstract

本发明涉及封闭型多异氰酸酯交联剂、其生产方法及其在1K烤漆,特别是OEM清漆(原始设备材料,底漆)中的用途。

Description

用丙二酸酯和三唑混合封闭的、含甲醛的 1，6-二异氰酸根络环己烷三聚体的稳定化方法
本发明涉及封闭型多异氰酸酯交联剂、其生产方法及其在单组分烤漆，特别是0EM清漆(原始设备材料，底漆)中的用途。
众所周知，封闭型多异氰酸酯被用作改进用于汽车清漆涂料中的单组分烤漆的添加剂。利用封闭型多异氰酸酯可以比较满意地达到改进的漆工艺性能的严格要求。然而，利用所有现有原材料都不能实现诸如最大值达140℃的低的烘烤温度或过度烘干时减少受热泛黄等其它性能。
最重要的工业用漆多异氰酸酯基于1，6-二异氰酸根络己烷(HDI)。当要求最大解封温度为140℃时，现有的工业规模用于多异氰酸酯的封闭剂为丙二酸酯和1，2，4-三唑。因为产物结晶析出，所以基于HDI的多异氰酸酯与丙二酸酯或1，2，4-三唑的结合，或如下文给出的对比实施例所示，与丙二酸酯/1，2，4-三唑混合物的结合，都不能导致能够稳定贮藏的有用的液态漆用交联剂。从EP-A600314已经公知丙二酸酯封闭的HDI多异氰酸酯有结晶的倾向，从EP-A654490和741157公知三唑封闭的多异氰酸酯有结晶的倾向。
本发明的目的是改进基于HDI的并用丙二酸酯和三唑的混合物封闭的多异氰酸酯，以形成用于单组分烤漆的在溶剂中不结晶的液态交联剂。
利用下述封闭型多异氰酸酯已可达到此目的。
本发明涉及脂肪族的和/或环脂族的多异氰酸酯，其中
A)5-95，优选70至30当量％的异氰酸基团是用酸性CH酯封闭(反应)的，
B)5-95，优选70至30当量％的异氰酸基团是用1，2，4-三唑封闭(反应)的，及
C)0-10当量％的异氰酸基团是用不同于A)和B)的封闭剂封闭(反应)的，其特征在于，含有相对于100当量％封闭的NCO基团0.05至1.0摩尔的结合(eingebauter)形式的甲醛。
本发明也涉及由下列物质生产本发明的非结晶的封闭型多异氰酸酯的方法：
a)100当量％的脂肪族的和/或环脂族的多异氰酸酯组分，
b)5-95，优选70至30当量％的选自酸性CH酯的封闭剂，
c)5-95，优选70至30当量％的1，2，4-三唑，
d)0-10当量％的不同于b)和c)的封闭剂，及
e)0.05-1.0摩尔的甲醛，其特征在于，在所存在的NCO基团完全反应之后，加入甲醛和催化量的碱，并让其反应掉。
本发明的非结晶封闭型多异氰酸酯可以优选含有防止受热泛黄的稳定剂，其为0.1-5.0％(重量)的含有式(I)结构单元的酰肼和0.1-5.0％(重量)的含有式(II)结构单元的“HALS胺”，
Figure A9981417200042
例如，从EP-A829500公知此种类型的稳定剂。
最后，本发明涉及本发明的封闭型多异氰酸酯作为聚氨酯烤漆如汽车清漆中有机多羟基化合物的交联剂的用途。
甲醛的含量是所要求保护的多异氰酸酯交联剂的发明的必要特征。令人惊讶地，甲醛显示出两种作用方式：第一，它防止封闭型多异氰酸酯结晶，特别是如果多异氰酸酯组分是基于HDI时；第二，它增加了封闭型多异氰酸酯对受热泛黄的抗性。
每100当量％封闭型多异氰酸酯优选使用0.1至0.4摩尔的多聚甲醛，并通过用催化剂如甲醇钠反应引入。这是相当于相对封闭型多异氰酸酯约0.8至5.0％(重量)的甲醛。非常特别优选相对于封闭型多异氰酸酯2.0至3.0％(重量)的甲醛含量。
本发明所述的方法如下进行：
将多异氰酸酯组分任选地与少量溶剂如1-甲氧基-2-丙基乙酸酯(MPA)一起加入反应器中，在大约50℃下，将酸性CH酯如丙二酸酯作为与约2％的30％甲醇钠溶液的混合物加入其中，在70-90℃下反应给出计算的NCO含量。之后，加入溶于另外的MPA的计算量的1，2，4-三唑，并在约90℃下反应完，以至不再能检测出NCO。将该批料冷却至大约45℃，将含相对多聚甲醛约3％的多聚甲醛澄清溶液加入含有作为碱的30％甲醇钠溶液和异丁醇的混合物中，随后，于45℃下搅拌约1小时。在此过程中，甲醛被掺入了；游离甲醛的含量在分析检测限度内。将相对该批料约0.5％的二丁基磷酸酯加入其中，以其将pH值调节至约7.5-7.0。根据本发明的一个具体实施方案，除了此澄清溶液外，还可加入其它阻止受热泛黄的稳定剂。
本发明的封闭型多异氰酸酯所基于的多异氰酸酯是公知的、含有脂肪族和/或环脂族和/或芳香族结合的异氰酸酯基团且其异氰酸酯含量为7至30，优选12至25％(重量)的漆用多异氰酸酯。
优选使用的多异氰酸酯为本领域公知的漆用多异氰酸酯，其包含缩二脲-、异氰脲酸酯-、尿烷-、脲基甲酸酯-和/或uretdione-基团并基于1，6-二异氰酸根络己烷(HDI)、1-异氰酸根络-3，3，5-三甲基-5-异氰酸根络甲基环己烷(IPDI)和/或双-(4-异氰酸根络环己基)甲烷(H12MDI或Desmodur W/Bayer AG)。此外，作为多异氰酸酯组分，也可以使用不对称三聚的、因此除了含异氰脲酸酯外还含亚氨基噁二嗪二酮基团的并基于1，6-二异氰酸根络己烷的漆用多异氰酸酯，如在EP-A798299中所描述的那些。
也可以使用基于其它异氰酸酯的多异氰酸酯，如基于1，4-二异氰酸根合丁烷、2，4-或2，6-二异氰酸根合-1-甲基-环己烷、2，5-和/或2，6-双异氰酸根络降冰片烷、3-和/或4-异氰酸甲酯基-1-甲基环己烷、1，4-双-(2-异氰酸根络-丙-1-基)苯、1，3-二异氰酸根合甲基苯或1，3-或1，4-双异氰酸根络甲基环己烷。
然而，非常特别优选用作多异氰酸酯组分的物质是含异氰脲酸酯基团的基于1，6-二异氰酸根络己烷的多异氰酸酯。
首先用作封闭组分的物质包括酸性CH酯，如丙二酸二乙基酯、乙酸乙酯和/或其甲基、异丙基、异丁基或叔丁基衍生物。优选丙二酸二乙基酯。其次，1，2，4-三唑用于所说的封闭混合物中。由1摩尔水合肼与至少2摩尔甲酰胺工业化大规模地生产1，2，4-三唑。酸性CH酯和1，2，4-三唑的用量可以各自为5-95当量％，优选20-80当量％。
下述物质可以一起用作另外的封闭剂，其量最多50当量％，优选最多20当量％：肟如丁酮肟、仲胺如二异丙基胺、酸性NH杂环如咪唑或3，5-二甲基吡唑或内酰胺如ε-己内酰胺。
从EP-A0829500公知的稳定剂可以用作附加的稳定组分。与此相关的优选物质有式(Ia)酰肼(分子量236)它可容易地由水合肼对2摩尔碳酸亚丙酯加成获得，以及氮原子没有被取代的HALS胺Tinuvin770DF(Novartis生产)。优选使用3至6％(重量)的前一种稳定剂，而优选使用0.5至1.5％(重量)后一种稳定剂，用量都是相对封闭型多异氰酸酯。
可以使用的溶剂是在聚氨酯化学中公知的且对NCO基团是惰性的溶剂，如1-甲氧基-2-丙基-乙酸酯、石脑油100溶剂或乙酸丁酯。如果NCO基团是封闭的，也优选使用醇如异丁醇以促进与封闭剂的醇残基的酯基转移作用。
参照下述实施例说明本发明多异氰酸酯交联剂的优点，也就是其优良的贮藏寿命，即没有结晶，降低的受热泛黄性及优良的漆工艺性能。实施例实施例1(根据本发明)
利用相对于封闭型多异氰酸酯固体物含量3.0％的甲醛使混合物封闭的多异氰酸酯稳定。相对100当量％的NCO基团，封闭剂的比率对应于丙二酸酯：三唑＝40：60当量％。配料200.0g     (1当量)    基于含NCO量约21％的1，6-二异
                  氰酸根络己烷(HDI)的含异氰脲
                  酸酯的漆用多异氰酸酯64.0g     (0.4mol)    丙二酸二乙酯41.4g     (0.6mol)    1，2，4-三唑9.0g      (0.3mol)    多聚甲醛65.2g                 酸甲氧基丙基酯65.2g                 异丁醇434.8g(1.0当量)       封闭的NCO基团
                  固体物含量：   70％
                  封闭的NCO含量：9.6％
                  23℃时粘度：   约6000mPas
                  外观：         透明，几乎无色
                  NCO当量：      435g实验
将多异氰酸酯和乙酸甲氧基丙基酯加入反应器中，并将其加热至约50℃。搅拌此溶液，并将丙二酸酯与1.2g甲醇钠溶液(30％甲醇溶液)的混合物加入其中，随后将配料在70℃下搅拌2小时，直到NCO含量少于计算值的7.6％为止。接着，将无色三唑薄片加入其中，将内部温度升高至90℃，随后将配料搅拌约3小时，直到不再能检测出NCO基团为止。将配料冷却至约45℃，将多聚甲醛、异丁醇和0.3g甲醇钠溶液(30％)的溶液加入其中，随后在40-45℃下搅拌1小时。最后，将2.1g磷酸二丁基酯加入其中，于是，得到透明、几乎无色的封闭型多异氰酸酯交联剂溶液，其可以稳定贮藏6个月。
实施例2(对比实施例)
除了不用甲醛对封闭型多异氰酸酯改性外，本实施例所用物质种类和数量与实施例1相同。这导致产品在室温下贮藏1周后就开始结晶析出。因此，此封闭型多异氰酸酯不可以用作能够稳定贮藏的单组分漆配方。
实施例3(根据本发明)
利用相对于封闭型多异氰酸酯固体物含量2.7％的稳定剂使混合物封闭的多异氰酸酯稳定。另外将两种其它稳定剂(参见EP-A829500A2)，也就是2.0％上述的酰肼和1.0％HALS胺，与封闭型多异氰酸酯溶液混合。配料300.0g    (1.5当量)     基于含NCO量约21％、23℃粘度约
                    3000mPas及官能度约为3.5的
                    1，6-二异氰酸根络己烷的含异氰
                    脲酸酯的漆用多异氰酸酯120.0g    (0.75mo1)     丙二酸二乙基酯51.7g     (0.75mol)     1，2，4-三唑13.5g     (0.45mol)     多聚甲醛4.9g      (1％/固体物)  Tinuvin770DF(Novartis AG)9.8g      (2％/固体物)  试验所述的分子量为236的酰肼加
                    成产物，包含摩尔水合肼和2摩尔
                    碳酸亚丙酯107.8g                  乙酸甲氧基丙基酯107.8g                  异丁醇715.5g                  封闭NCO基团(1.5当量)
                    固体物含量：     70％
                    封闭的NCO含量：  8.8％
                    粘度(23℃)：     约5000mPas
                    外观：           透明，哈森色度
                                     60
                    NCO当量(封闭的)：477g实验
将多异氰酸酯和乙酸甲氧基丙基酯加入反应器中。在约50℃下搅拌，并将丙二酸二乙基酯与约2％即2.4g甲醇钠溶液(30％甲醇溶液)的混合物分批加入其中。将配料温度升高至70℃并搅拌约1个半小时，直到NCO含量少于计算值的5.95％为止。接着，将无色三唑薄片加入其中，将内部温度升高至90℃，随后将配料搅拌约3小时，直到不再能检测出NCO基团为止(IR光谱)。将配料冷却至45℃，将多聚甲醛、异丁醇和0.5g甲醇钠溶液(30％)的溶液加入其中，随后在45℃下将配料搅拌约1小时。然后，将Tinuvin770DF，也就是上述的酰肼加成产物与剩下的异丁醇一起加入其中。最后，将3.5g磷酸二丁基酯搅拌加入其中，于是，得到透明、几乎无色(哈森色度60)的可以稳定贮藏且含477gNCO当量(封闭的)的混合物封闭的多异氰酸酯交联剂溶液。
实施例4(用途实施例)
将实施例3得到的交联剂与下述组分混合得到透明清漆。将此透明清漆应用于涂有市售的底漆如Cologne的Spies&Hecker供应的底漆的试验板条上，产生厚度约120至150μm的湿涂层，将其烘烤干并按下表说明进行试验。配方
37.2g DesmophenA VP LS 2009/1，70％在BA中的溶液
      (Bayer AG)，OH当量565g
31.4g 实施例3中的交联剂，
      混合物比率：NCO∶OH＝1∶1
0.5g  二月桂酸二丁基锡100％
11.2g 乙酸甲氧基丙基酯/石脑油100(1/1)漆工艺试验结果23秒完成时间喷涂的固体                   约50％烘烤条件                                30分钟，140℃摆杆阻尼(振动)1)                       143
    (s)                             200耐溶剂性(注*)2)(X/MPA/EA/AC)1分钟                      1234
         5分钟                      2244耐化学品性(℃)3)(梯度烘箱法)                            36
树脂                                36
刹车油                              36
胰液素，50％                        36
NaOH，1％                           36
H2SO4，1％                       41FAM：10分钟(注*)                       2受热泛黄4)LM底漆上的清漆
初始泛黄(b)                         0.1
160℃下过度烘干30分钟后泛黄(Δb)     1.9H2O底漆上的清漆
初始泛黄(b)                         -1.2
160℃下过度烘干30分钟后泛黄(Δb)     1.2抗刮性(实验室连续冲洗)5)
初始20°光泽度                      90.8
10次冲洗循环后光泽度损失             23.2*)0-好；5-差
可以看出，本发明所述的体系显示出总体上优良的漆性能。
1)DIN ISO 1522
2)拜尔试验方法；根据DIN 53230估算
3)根据Daimler-Benz试验方法
4)DIN 6174(CIELAB)
5)根据德国表面处理协会(DFO)(杜塞尔多夫)试验方法

Claims (4)

1.脂肪族的和/或环脂族的多异氰酸酯，其中
A)5-95当量％异氰酸基团是用酸性CH酯封闭(反应)的，
B)5-95当量％异氰酸基团是用1，2，4-三唑封闭(反应)的，及
C)0-10当量％异氰酸基团是用不同于A)和B)的封闭剂封闭(反应)的，其特征在于：含有相对于100当量％封闭的NCO基团0.05至1.0摩尔的结合形式的甲醛。
2.由下列物质制备本发明所述的非结晶封闭型多异氰酸酯的方法：
a)100当量％脂肪族的和/或环脂族的多异氰酸酯组分，
b)5-95当量％来自酸性CH酯的封闭剂，
c)5-95当量％1，2，4-三唑，
d)0-10当量％不同于b)和c)的封闭剂，及
e)0.05-1.0摩尔甲醛，其特征在于：在所存在的NCO基团完全反应之后，加入甲醛和催化量的碱，并让其反应掉。
3.权利要求1所述的封闭型多异氰酸酯，其特征在于：其含有防止受热泛黄的稳定剂，其为0.1-5.0％(重量)含式(I)结构单元的酰肼和0.1-5.0％(重量)含式(II)结构单元的“HALS胺”，
Figure A9981417200021
Figure A9981417200022
4.权利要求1所述的封闭型多异氰酸酯作为聚氨酯烤漆如汽车清漆中有机多羟基化合物的交联剂的用途。
CN99814172A 1998-12-07 1999-11-24 用丙二酸酯和三唑混合封闭的、含甲醛的1,6－二异氰酸根络环己烷三聚体的稳定化方法 Pending CN1329625A (zh)

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DE1998156968 DE19856968A1 (de) 1998-12-10 1998-12-10 Malonester/Triazolmischblockiertes HDI-Trimerisat/Formaldehydstabilisierung
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DE19750186A1 (de) * 1997-11-13 1999-05-20 Bayer Ag Hydrophilierungsmittel, ein Verfahren zu dessen Herstellung sowie dessen Verwendung als Dispergator für wäßrige Polyurethan-Dispersionen
DE19813352A1 (de) * 1998-03-26 1999-09-30 Bayer Ag Malonesterblockierte Polyisocyanate mit Formaldehyd gegen Thermovergilbung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100349942C (zh) * 2002-01-17 2007-11-21 拜尔材料科学股份公司 稳定化的交联剂水分散体
CN106471028A (zh) * 2015-05-21 2017-03-01 萨普股份责任有限公司 聚氨酯组合物

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