CN1005718B - 具有极低甲醛对尿素摩尔比的脲甲醛树脂的制备方法 - Google Patents
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Abstract
尿素与甲醛以约1∶2的摩尔比相混合。在pH7.0至7.4及温度80和85℃之间使混合物结合30分钟。在pH4.8至5.8和同样温度继续缩合直至粘度达到15和50mpa.s之间的数值。藉添加尿素调节尿素对甲醛的摩尔比到1∶1.80至1∶1.90的数值。在酸性条件下于相同温度继续缩合。直至粘度达到35至80ma.s。于pH5.8至6.5,藉添加尿素调整尿素对甲醛摩尔比至1.0∶1.0和1.0∶1.30之间的数值。让温度自由地下降。当温度已降至低于50℃,调节pH值到7.0至8.0。
Description
普通的脲甲醛树脂通常以二阶段制造。尿素与甲醛在中性或略带碱性的条件下以甲醛对尿素2∶1或更大的摩尔比混合,加热混合物至差不多回流温度以保证生成羟甲基脲。然后将这样得到的溶液的pH调节到6.5至5.0的范围并加热至回流温度(90至95℃)。继续缩合直至达到所希望的缩合程度。可凭藉下列现象观察聚合的进程:
a)初始,在冷却溶液时生成一白色固体沉淀。
b)当聚合作用继续进行,析出沉淀的温度下降,直至最终达到这样一点,缩合产品在室温亦不再沉淀。反应产品完全溶于冷水中。
c)在进一步聚合时,溶液粘度增高,耐水性减小,而且浆液凝固形成一不溶和不可逆凝胶。
在胶凝点以前,亦即达到了期望的聚合程度,对此各制造厂互不相同,藉加入碱直至浆液略带碱性以阻止反应。或者恰在真空蒸发除去水分之前或者在其后混合足够的尿素入浆液使得甲醛对尿素的最终摩尔比为1.5或更大,亦可一部分尿素在真空蒸发除去水分之前加入,其余则在其后加入。然后冷却产品至约20℃而于下一天已可使用。
本发明的目的为提供一种游离甲醛含量极低的脲甲醛以消除使用此树脂特别是在生产胶合板和碎料板时对人潜在的健康危害。
本发明的另一目的是提供一种脲甲醛树脂适宜作为粘合剂用于制造碎料板和胶合板型的面板,那种面板具有极低的甲醛散发,因此对最终的使用者不会发生危害健康的问题,而且还满足对于所生产面板性质的全部要求。
本发明更进一步的目的是提供一种脲甲醛树脂除了上述的性质外,它具有在20℃的贮藏稳定性四星期和一短的硬化时间(这表示它是活性的)以及能以通常的数量用于生产碎料板和胶合板型的面板。
以前的工艺通常以二个阶段制造树脂,它具有相当高的甲醛对尿素摩尔比(1.25或更高)和相当高的游离甲醛浓度。本发明的方法,其中尿素以三份或更多份加入一连续操作中,产生具有极低的甲醛对尿素摩尔比(1.0=1.0至1.15∶1.0)和极低游离甲醛浓度的脲甲醛树脂。这种树脂适宜于作为粘合剂用于制造碎料板和胶合板型的面板,那种面板的甲醛散发极低。
本发明的方法消除了由于使用平常的脲甲醛树脂引起对健康的潜在危险,在生产胶合板和碎料板的工厂使用它而导致工人经常处于来自此树脂的高游离甲醛散发之中,以及在家庭,办公室等等的最终使用者经常暴露在来自用此树脂生产的面板的高游离甲醛散发之中。
特殊的反应条件影响所生产树脂在羟甲基团,亚甲基团,亚甲基键,亚甲基-醚键和分子量以及分子量分布等方面的结构特征。
已知在中性或温和的碱性条件下一羟甲基脲和二羟甲基脲分别以甲醛对尿素的摩尔比1.0∶1.0或2∶1优先地形成。在稀酸溶液中,羟甲基脲的羟甲基和酰胺基会进行缩合反应形成亚甲基键。在弱酸性介质(pH4至7)中,羟甲基团亦能互相反应形成亚甲基-醚键。
在交联以前,甲醛树脂的一般结构可以下式来说明:
其中R为氢或一羟甲基而n为聚合度。如果R是氢,增加聚合度会降低树脂的水混合溶性和延长树脂的硬化时间。另一方面,
若R是一羟甲基(-CH2OH),在增加聚合度时树脂的胶态稳定性和水混溶性会显著地改善并且此种树脂具有比较短的硬化时间。为了良好的物理性质,诸如强度,粘性和粘合力,需要高的聚合度。
为了制造具有良好稳定性;分散性的粘合性以及低的游离甲醛含量的脲甲醛树脂曾提出过各种方法。然而期望的各种性质的最佳协调通常难以达到。例如采用低的甲醛对尿素摩尔比生产出低甲醛含量的树脂,但它具有不好的稳定性和长的凝结时间。
本发明克服了以前工艺的缺点。本发明方法生产的脲甲醛树脂具有低的甲醛对尿素摩尔比和低的游离甲醛浓度连同良好的胶态稳定性和较高的凝固速率。此外,依照本发明生产的树脂具有适合于制造碎料板和胶合板型面板的粘合性质。
本发明方法的特征为
a)尿素与甲醛以约1.0∶2.0的摩尔比混合,并在碱性条件下将混合物加热至80和85℃之间的温度;
b)热后调节pH值至7.0至7.4的范围,并于同样温度下使混合物缩合30分钟。
c)然后调节pH值到4.8至5.8的范围,在酸性条件下于同样温度继续缩合至粘度度达到15至50mpa.s之间的数值;
d)加入尿素调整尿素对甲醛摩尔比到1.0∶1.70至1.0∶1.9的范围内,并在酸性条件下于相同温度继续缩合,直至粘度达到35至80mpa.s。
e)然后调节pH值到5.8至6.5的范围内,并藉加入尿素使最终的尿素对甲醛的摩尔比调整到1.0∶1.0和1.0∶1.30之间的数值,最好在1∶1、105至1∶1.12的范围内,此后冷却缩合物,以及。
f)当温度降至低于50℃时,调整最终的pH值到7.0至8.0的范围内。
本发明的方法可实现如下:
于第一阶段,以稀的氢氧化纳溶液调节一已知量的甲醛水溶液pH值7.2至7.6,于是以2.0∶1.0的甲醛对尿素摩尔比混以尿素。将如此获得的溶液加热到温度80至85℃。一达到此温度范围即调整反应混合物使pH至7.0至7.4的范围,于同样温度进行反应20至40分钟,然后以甲酸溶液酸化反应混合物使pH为4.8至5.8,同时仍保持温度在80至85℃。在此温度继续缩合反应直至反应混合物的粘度以布鲁克菲尔德粘度计(Brookfield Viscomerter)(心轴№.1)于65℃测得为15至35mpa.s。
在方法的第二阶段中,添加尿素使甲醛对尿素总摩尔比达1.70∶1.0至1.90∶1.0。在同样条件下继续缩合反应,直至反应混合物具有65℃测得的布鲁克菲尔德粘度在35至80mpa.s的范围。一但获得期望的粘度,即以稀氢氧化钠溶液调节反应混合物的pH值到5.8至6.5的范围内。
在第三阶段中,藉添加尿素调整最终的总甲醛对总尿素的摩尔比为1.0∶1.0至1.30∶1.0。停止加热,并再搅拌混合物20至30分钟。将反应混合物冷却至60℃左右。
在真空中于54至57℃将树脂蒸发至约66%固体,然后冷却至低于40℃。于此温度最终调整*脂的pH至约7.4。产品最好贮藏20℃左右的温度下。于下一天可使用。
反应器装有一搅拌器,在缩合过程中连续地搅拌反应混合物。本发明方法所生产的树脂其特征为它们的甲醛对尿素摩尔比十分低,它低于以前工艺中任何已知的稳定的树脂。可以制造甲醛对尿素摩尔比低达1.0∶1.0的树脂。不管此极低的摩尔比,树脂在足够长的时间内仍然稳定,以及它们的凝结时间是比较短的。最重要的特点为用本发明方法生产的树脂具有的游离甲醛含量等于或低于0.15%这是以前工艺所不能达到的。
本发明的方法是脲甲醛树脂工艺的一大突破,因为以前工艺的低甲醛对尿素摩尔比树脂遭受差的稳定性和不良反应性的损害。
用本发明方法制备的树脂所生产的刨花板和胶合板面板具有良好的机械性质和抗水性。此外,这些面板的游离甲醛含量低于DIN标准E1=每100g板10mg。
下列例子说明本发明。
例1
采用一装有搅拌器的反应器。在整个缩合过程中将反应混合物搅拌。
将2500kg40%的甲醛水溶液加入反应器并在不停搅拌下以40%氢氧化钠溶液中和至pH7.4。加入1000kg尿素,然后加热混合物至温度82至83℃。于此温度调节pH至7.2。在这些条件下进行缩合30分钟。此后以甲醛溶液调节pH至5.4。在同样温度继续缩合直至反应混合物的粘度以布鲁克菲尔德粘度计(心轴№.1)于65℃测得为28mPa.s为止。
立即加入第二份100kg的尿素,继续在同样温度下缩合直至反应混合物具有于65℃测得的布鲁克菲尔德粘度(心轴№.1)约为68mpa.s。然后藉加入40%氢氧化钠溶液调节反应混合物之pH至6.1。
加入第三份640kg的尿素,这样最终的总甲醛对总尿素的摩尔比为1.15∶1。停止加热,而只在搅拌下进行25分钟的最后阶段的缩合。至此时间末了,反应混合物的温度已降至约60℃。
于部分真空下在54至57℃蒸发反应混合物至65.8%固体。然后冷却至约38℃,并且40%氢氧化溶液调节最终pH至7.1,产品储藏于20℃。
例2
在一装有搅拌器的反应器中,在不断搅拌下首先以40%氢氧化钠溶溶中和2500kg40%的甲醛水溶液至pH7.4,然后加入1000kg尿素,于是加热混合物至85℃。在此温度,调节pH至7.1,然后使反应混合物缩合30分钟。此后用甲酸溶液调节pH至4.8。继续缩合直到反应混合物具有在65℃测得的布鲁克菲尔德粘度(心轴№.1)为24mpa.s。
此后,加入第二份尿素110kg。继续缩合直至反应混合物具有于65℃测得的布鲁克菲尔德粘度(心轴№.1)约为40mpa.s。
在此阶段,以40%氢氧化钠溶液调节pH至5.8。
加入第三份尿素223kg,同时保持反应温度85℃。继续缩合直至反应混合物具有于65℃测得的布鲁克菲尔德粘度(心轴№.1)约为50mpa.s。以40%氢氧化钠溶液调节pH至6.2。然后停止加热。
加入第四份尿素467kg这样总甲醛对总尿素的最终摩尔比为1.10∶1让温度自由地降落20分钟。使反应混合物冷却至约35℃,然后用40%氢氧化钠溶液调节pH至7.2。将这样得到的最终的树脂冷却至20℃并于该温度贮藏。因为没有发生过脱水过程树脂适用于胶合板的生产。
将反应混合物搅拌是贯穿在以上的缩合过程的。
在例1和2中得到的脲甲醛树脂的性质显示于表Ⅰ。用亚硫酸盐法测定了游离甲醛的含量。它在二批树脂中均低于0.15%。
用例1和2的甲醛树脂生产的刨花板面的性质示于表Ⅱ
进行了数次以本发明方法制造的树脂粘合热带硬木树种单板成3-层胶合板的试验。由采用上述树脂的数种典型胶水混合物得到的结果显示表Ⅲ。
例3
此例将碎料板生产中采用本发明方法制备的低游离甲醛树脂和采用以前工艺的甲醛树脂相比较。
所用胶水配方如下:
1 2
以前工艺的甲醛树脂65%
其摩尔比为F∶U1.27∶1(g) 3077 -
如例1制备的甲醛树脂65%
其摩尔比为F∶U1.15∶1(g) - 3077
氨25°波美(g) 10 -
硬化剂(15%氯化铵溶液)(g) 400 400
石腊乳剂50%(g) 250 250
水(g) 263 263
总计(g) 4000 4000
胶凝时(秒) 80 76
将这些配方各自喷在25kg碎木片上,在实验室中压制单层板以10,9和8秒/毫米压制。板的厚度为17.3毫米。压制温度200℃而压力为35kg/cm2。所制板的尺寸为40×56cm。
所得结果之平均值报告于下表。
1 2
密度(kg/m3) 691 681
抗弯强度(N/mm2) 19.6 18.9
抗张强度(N/mm2) 0.56 0.55
2小时厚度膨胀(%) 9.8 10.5
24小时厚度膨胀(%) 25.5 26.0
游离甲醛(mg/100g干板) 18.5 8.1
上述结果证明以本发明方法制备的树脂所生产的板具有很低的游离甲醛含量。实际上它们出产的木板具有低于10mg/100g干板的游离甲醛含量(因而,属于DIN标准E1)。这些板的机械性质与以前工艺的树脂所制的板比较毫不降低。
表Ⅰ
表Ⅱ
表Ⅲ
Claims (9)
1、一具有很低甲醛对尿素摩尔比的脲甲醛树脂制备方法,其特征为:
a)尿素与甲醛以1.0∶2.0尿素对甲醛摩尔比相混合,并在碱性条件下加热混合物至80和85℃之间的温度;
b)然后调节pH值到7.0至7.4的范围,于是在同样温度使混合物缩和30分钟;
c)然后调节pH值到4.8至5.8的范围,在酸性条件下于同样温度继续缩合直至粘度达到15至50mpa.s之间的数值;
d)藉添加尿素调节尿素对甲醛的摩尔比值到1.0∶1.7至1.0∶1.90的范围,在酸性条件下于同样温度继续缩合,直至粘度达到35至80mpa.s的范围;
e)然后调节pH值到5.8至6.5的范围,并藉添加尿素调整尿素对甲醛的最终摩尔比至1.0∶1.0和1.0∶1.30之间的值,此后让温度下降,以及
f)当温度已降至50℃以下,调节最终pH值到7.0至8.0的范围。
2、依照权利要求1的方法,其特征为在步骤e)中调节尿素对甲醛的最终摩尔比到1.0∶1.105至1.0∶1.12范围内的数值。
3、依照权利要求1或2的任一方法,其特征为在步骤f)中调节最终pH至7.2。
Priority Applications (34)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB08332962A GB2150939B (en) | 1983-12-09 | 1983-12-09 | A process for preparing urea-formaldehyde resins |
ZA849088A ZA849088B (en) | 1983-12-09 | 1984-11-21 | A process for preparing a urea-formaldehyde resin having a very low mole ratio of formaldehyde to urea |
CA000468663A CA1242840A (en) | 1983-12-09 | 1984-11-27 | Process for preparing a urea-formaldehyde resin having a very low mole ratio of formaldehyde to urea |
IL73647A IL73647A (en) | 1983-12-09 | 1984-11-27 | Preparation of urea-formaldehyde resin having a very low mole ratio of formaldehyde to urea |
AT0375584A AT383355B (de) | 1983-12-09 | 1984-11-27 | Verfahren zur herstellung eines harnstoff-formaldehyd-harzes mit einem sehr niedrigen molverhaeltnis von formaldehyd zu harnstoff |
US06/675,195 US4603191A (en) | 1983-12-09 | 1984-11-27 | Process for preparing a urea-formaldehyde resin having a very low mole ratio of formaldehyde to urea |
FI844697A FI79332B (fi) | 1983-12-09 | 1984-11-29 | Foerfarande foer framstaellning av ett urea-formaldehydharts som har ett mycket laogt molfoerhallande av formaldehyd till urea. |
AU36098/84A AU569207B2 (en) | 1983-12-09 | 1984-11-30 | Urea-formaldehyde resin |
NZ210396A NZ210396A (en) | 1983-12-09 | 1984-11-30 | Preparation of urea-formaldehyde resins |
CH5733/84A CH663213A5 (de) | 1983-12-09 | 1984-11-30 | Verfahren zur herstellung eines harnstoff-formaldehyd-harzes mit einem molverhaeltnis von formaldehyd zu harnstoff von 1,0:1.0 bis 1,15:1,0. |
GR81139A GR81139B (en) | 1983-12-09 | 1984-12-03 | Process for preparing a urea-fomaldehyde resin having a very low mole ratio of fomaldehyde to urea |
DE19843444203 DE3444203A1 (de) | 1983-12-09 | 1984-12-04 | Verfahren zur herstellung eines harnstoff-formaldehyd-harzes mit einem sehr niedrigen molverhaeltnis von formaldehyd zu harnstoff |
CS849389A CS256385B2 (en) | 1983-12-09 | 1984-12-05 | Method of urea formaldehyde resin preparation with superlow formaldehyde-urea molecular ratio |
BG8467779A BG43694A3 (en) | 1983-12-09 | 1984-12-05 | Method for preparing of carbamide formaldehydic resin |
RO84116534A RO90378A (ro) | 1983-12-09 | 1984-12-05 | Procedeu pentru prepararea unei rasini ureoformaldehidice |
SE8406166A SE458363B (sv) | 1983-12-09 | 1984-12-05 | Foerfarande foer framstaellning av ett karbamid-formaldehydharts med ett mycket laagt molfoerhaallande mellan formaldehyd och karbamid |
NL8403699A NL8403699A (nl) | 1983-12-09 | 1984-12-05 | Werkwijze voor het bereiden van een ureumformaldehydehars met een zeer lage molverhouding van formaldehyde tot ureum. |
DD84270386A DD235877A5 (de) | 1983-12-09 | 1984-12-06 | Verfahren zur herstellung eines kunststoff-formalalhyd-harzes |
NO844905A NO160852B (no) | 1983-12-09 | 1984-12-07 | Fremgangsm te for fremstilling av en urea-formaldehks med meget lavt molforhold mellom formaldehyd og urea. |
PL1984250797A PL142931B1 (en) | 1983-12-09 | 1984-12-07 | Method of obtaining urea-formaldehyde resins |
FR848418720A FR2556351B1 (fr) | 1983-12-09 | 1984-12-07 | Procede de preparation d'une resine uree formaldehyde presentant un rapport molaire tres faible du formaldehyde a l'uree |
SU843823258A SU1454254A3 (ru) | 1983-12-09 | 1984-12-07 | Способ получени мочевиноформальдегидной смолы |
PT79643A PT79643B (en) | 1983-12-09 | 1984-12-07 | A process for preparing a urea-formaldehyde resin having a very low mole ratio of formaldehyde to urea |
YU2076/84A YU44480B (en) | 1983-12-09 | 1984-12-07 | Process for making carbamide-formaldehyde resin with very basis of hard polyurethane foam low formaldehyde to carbamide content |
LU85673A LU85673A1 (de) | 1983-12-09 | 1984-12-07 | Verfahren zur herstellung eines harnstoff-formaldehyd-harzes mit einem sehr niedrigen molverhaeltnis von formaldehyd zu harnstoff |
ES538374A ES8600337A1 (es) | 1983-12-09 | 1984-12-07 | Un procedimiento para preparar una resina de urea-formaldehido |
BE0/214136A BE901236A (fr) | 1983-12-09 | 1984-12-07 | Procede de preparation d'une resine uree-formaldehyde presentant un rapport molaire tres faible du formaldehyde a l'uree. |
BR8406271A BR8406271A (pt) | 1983-12-09 | 1984-12-07 | Processo para a preparacao de uma resina de ureia/formaldeido com uma relacao molar muito baixa de formaldeido/ureia |
IT49269/84A IT1178271B (it) | 1983-12-09 | 1984-12-07 | Procedimento per preparare una resina urea-formaldeidica a basso rapporto fra formaldeide ed urea |
HU844544A HU194921B (en) | 1983-12-09 | 1984-12-07 | Process for production of carbamide-formaldehide resin with cca 1 : 1 mole proportion of these two components |
DK585284A DK585284A (da) | 1983-12-09 | 1984-12-07 | Fremgangsmaade til fremstilling af en urea-formaldehydharpiks med meget lavt molforhold mellem formaldehyd og urea |
JP25985084A JPS6134010A (ja) | 1983-12-09 | 1984-12-08 | 尿素‐ホルムアルデヒド樹脂の製造法 |
CN85104298.8A CN1005718B (zh) | 1983-12-09 | 1985-06-04 | 具有极低甲醛对尿素摩尔比的脲甲醛树脂的制备方法 |
SG577/87A SG57787G (en) | 1983-12-09 | 1987-07-09 | A process for preparing a urea-formaldehyde resin having a very low mole ratio of formaldehyde to urea |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB08332962A GB2150939B (en) | 1983-12-09 | 1983-12-09 | A process for preparing urea-formaldehyde resins |
CN85104298.8A CN1005718B (zh) | 1983-12-09 | 1985-06-04 | 具有极低甲醛对尿素摩尔比的脲甲醛树脂的制备方法 |
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Publication Number | Publication Date |
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CN85104298A CN85104298A (zh) | 1987-01-14 |
CN1005718B true CN1005718B (zh) | 1989-11-08 |
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CN85104298.8A Expired CN1005718B (zh) | 1983-12-09 | 1985-06-04 | 具有极低甲醛对尿素摩尔比的脲甲醛树脂的制备方法 |
Country Status (34)
Country | Link |
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US (1) | US4603191A (zh) |
JP (1) | JPS6134010A (zh) |
CN (1) | CN1005718B (zh) |
AT (1) | AT383355B (zh) |
AU (1) | AU569207B2 (zh) |
BE (1) | BE901236A (zh) |
BG (1) | BG43694A3 (zh) |
BR (1) | BR8406271A (zh) |
CA (1) | CA1242840A (zh) |
CH (1) | CH663213A5 (zh) |
CS (1) | CS256385B2 (zh) |
DD (1) | DD235877A5 (zh) |
DE (1) | DE3444203A1 (zh) |
DK (1) | DK585284A (zh) |
ES (1) | ES8600337A1 (zh) |
FI (1) | FI79332B (zh) |
FR (1) | FR2556351B1 (zh) |
GB (1) | GB2150939B (zh) |
GR (1) | GR81139B (zh) |
HU (1) | HU194921B (zh) |
IL (1) | IL73647A (zh) |
IT (1) | IT1178271B (zh) |
LU (1) | LU85673A1 (zh) |
NL (1) | NL8403699A (zh) |
NO (1) | NO160852B (zh) |
NZ (1) | NZ210396A (zh) |
PL (1) | PL142931B1 (zh) |
PT (1) | PT79643B (zh) |
RO (1) | RO90378A (zh) |
SE (1) | SE458363B (zh) |
SG (1) | SG57787G (zh) |
SU (1) | SU1454254A3 (zh) |
YU (1) | YU44480B (zh) |
ZA (1) | ZA849088B (zh) |
Cited By (1)
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CN101289567B (zh) * | 2007-04-16 | 2010-07-21 | 天津优宁福姆建筑节能科技开发有限公司 | 一种脲醛树脂发泡保温材料 |
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GB2192005B (en) * | 1986-06-27 | 1989-12-13 | Ciba Geigy Ag | Process for the preparation of urea-formaldehyde resins |
GB8715305D0 (en) * | 1987-06-30 | 1987-08-05 | Ciba Geigy Ag | Process |
FR2625204B1 (fr) * | 1987-12-23 | 1991-12-06 | Charbonnages Ste Chimique | Nouveau procede de fabrication des resines uree-formol |
FR2625207B1 (fr) * | 1987-12-23 | 1991-12-06 | Charbonnages Ste Chimique | Nouveau procede de preparation de resines aminoplastes a tres faible degagement de formol |
DD283732A7 (de) * | 1988-10-21 | 1990-10-24 | ������@�����`������@ ���@������� k�� | Verfahren zur herstellung eines reaktiven harnstoff-formaldehyd-harz-leimes |
US5110898A (en) * | 1988-11-28 | 1992-05-05 | Georgia-Pacific Corporation | Method for manufacturing amino-aldehyde compositions |
US4960856A (en) * | 1988-11-28 | 1990-10-02 | Georgia-Pacific Corporation | Urea-formaldehyde compositions and method of manufacture |
US5362842A (en) * | 1993-09-10 | 1994-11-08 | Georgia Pacific Resins, Inc. | Urea-formaldehyde resin composition and method of manufacture thereof |
EP0743331A4 (de) * | 1994-02-08 | 1997-01-07 | N T Predpr Ligand | Verfahren zum herstellen von einem carbamid-formaldehyd-harz und ein kondensat zu seiner herstellung |
US5674971A (en) * | 1995-06-06 | 1997-10-07 | Georgia-Pacific Resins, Inc. | Urea-formaldehyde resin composition and method of preparation thereof |
US5681917A (en) * | 1996-03-26 | 1997-10-28 | Georgia-Pacific Resins, Inc. | Low mole ratio melamine-urea-formaldehyde resin |
US5684118A (en) * | 1996-03-26 | 1997-11-04 | Georgia-Pacific Resins, Inc. | Method of scavenging formaldehyde using a low mole ratio melamine-urea-formaldehyde resin |
US6548625B2 (en) * | 2001-03-23 | 2003-04-15 | Cytec Technology Corp. | Stable liquid melamine urea formaldehyde resins, hardeners, adhesive compositions, and methods for making same |
CN100344720C (zh) * | 2006-03-30 | 2007-10-24 | 浙江林学院 | 环保型低成本脲醛树脂胶生产方法 |
CN101796116B (zh) * | 2007-09-21 | 2013-04-24 | 圣戈班磨料磨具有限公司 | 用于磨料产品的羟甲基三聚氰胺 |
US20090291286A1 (en) * | 2008-03-04 | 2009-11-26 | Ziming Shen | Laminate manufacturing system, method, and article of manufacture |
CN101245129B (zh) * | 2008-04-01 | 2010-06-02 | 河北大学 | 一种自升温生产脲醛树脂的方法 |
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DE2334380B1 (de) * | 1973-07-06 | 1974-09-05 | Basf Ag | Verfahren zur Herstellung eines Holzleims |
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IT1209203B (it) * | 1980-04-10 | 1989-07-16 | Montedison Spa | Collante ureico a basso sviluppo di formaldeide ed alto valore di tack. |
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-
1983
- 1983-12-09 GB GB08332962A patent/GB2150939B/en not_active Expired
-
1984
- 1984-11-21 ZA ZA849088A patent/ZA849088B/xx unknown
- 1984-11-27 AT AT0375584A patent/AT383355B/de not_active IP Right Cessation
- 1984-11-27 IL IL73647A patent/IL73647A/xx unknown
- 1984-11-27 US US06/675,195 patent/US4603191A/en not_active Expired - Fee Related
- 1984-11-27 CA CA000468663A patent/CA1242840A/en not_active Expired
- 1984-11-29 FI FI844697A patent/FI79332B/fi not_active Application Discontinuation
- 1984-11-30 CH CH5733/84A patent/CH663213A5/de not_active IP Right Cessation
- 1984-11-30 NZ NZ210396A patent/NZ210396A/en unknown
- 1984-11-30 AU AU36098/84A patent/AU569207B2/en not_active Ceased
- 1984-12-03 GR GR81139A patent/GR81139B/el unknown
- 1984-12-04 DE DE19843444203 patent/DE3444203A1/de not_active Withdrawn
- 1984-12-05 NL NL8403699A patent/NL8403699A/nl not_active Application Discontinuation
- 1984-12-05 BG BG8467779A patent/BG43694A3/xx unknown
- 1984-12-05 SE SE8406166A patent/SE458363B/sv unknown
- 1984-12-05 RO RO84116534A patent/RO90378A/ro unknown
- 1984-12-05 CS CS849389A patent/CS256385B2/cs unknown
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- 1984-12-07 PT PT79643A patent/PT79643B/pt unknown
- 1984-12-07 NO NO844905A patent/NO160852B/no unknown
- 1984-12-07 IT IT49269/84A patent/IT1178271B/it active
- 1984-12-07 YU YU2076/84A patent/YU44480B/xx unknown
- 1984-12-07 ES ES538374A patent/ES8600337A1/es not_active Expired
- 1984-12-07 FR FR848418720A patent/FR2556351B1/fr not_active Expired - Fee Related
- 1984-12-07 DK DK585284A patent/DK585284A/da unknown
- 1984-12-07 BE BE0/214136A patent/BE901236A/fr not_active IP Right Cessation
- 1984-12-07 SU SU843823258A patent/SU1454254A3/ru active
- 1984-12-07 HU HU844544A patent/HU194921B/hu not_active IP Right Cessation
- 1984-12-08 JP JP25985084A patent/JPS6134010A/ja active Granted
-
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Cited By (1)
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CN101289567B (zh) * | 2007-04-16 | 2010-07-21 | 天津优宁福姆建筑节能科技开发有限公司 | 一种脲醛树脂发泡保温材料 |
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