WO2016026341A1 - 一种抗划伤mdi及ipdi多聚物聚氨酯固化剂的制备方法 - Google Patents

一种抗划伤mdi及ipdi多聚物聚氨酯固化剂的制备方法 Download PDF

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WO2016026341A1
WO2016026341A1 PCT/CN2015/080484 CN2015080484W WO2016026341A1 WO 2016026341 A1 WO2016026341 A1 WO 2016026341A1 CN 2015080484 W CN2015080484 W CN 2015080484W WO 2016026341 A1 WO2016026341 A1 WO 2016026341A1
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curing agent
mdi
ipdi
scratch
polyester polyol
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PCT/CN2015/080484
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English (en)
French (fr)
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许钧强
康伦国
姚东生
阳京辉
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合众（佛山）化工有限公司
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to a preparation method of a polyurethane curing agent, in particular to an anti-scratch MDI and IPDI multi-polymer polyurethane curing agent.
  • the commonly used polymeric polyurethane curing agents in the market are MDI/TMP, MDI/HDI, MDI/TDI products containing toxic solvents such as xylene and ethyl acetate; the curing agent contains a certain amount of free monomers HDI and MDI, They are toxic chemicals, chemically active, highly volatile, have a strong pungent odor and tearing effect, stimulate the respiratory system after inhalation, cause headache bronchitis, severe death and serious pollution to the environment.
  • IPDI isophorone diisocyanate is an alicyclic isocyanate with lower IPDI reactivity than aromatic isocyanate, but IPDI reacts with hydroxyl groups 4 to 5 times faster than HDI and hydroxyl groups. Since diphenylmethane diisocyanate MDI has poor light resistance and yellowing resistance, its use is limited, and isophorone diisocyanate IPDI has excellent light stability, co-yellowing resistance and chemical resistance, but the cost is high. .
  • the present invention aims to provide a method for preparing an anti-scratch MDI and IPDI multipolymer polyurethane curing agent.
  • the present invention adopts the economical, low toxicity and superiority of isophorone diisocyanate IPDI of the diphenylmethane diisocyanate MDI to react with the low molecular weight polyester polyol to form MDI and IPDI.
  • Polymer polyurethane curing agent low molecular weight polyester polyol used in the present invention is carried out using phthalic anhydride, terephthalic acid, isophthalic acid or a derivative thereof with TMP and glycol
  • the esterification reaction is carried out;
  • the molecular structure of the MDI and IPDI multipolymer polyurethane curing agent made of the polyester polyol has a symmetrical aromatic ring structure and has rigidity, thereby improving scratch resistance, hardness and wear resistance;
  • Adding an appropriate amount of adipic acid or sebacic acid improves the flexibility of the film formation of the curing agent, reduces the viscosity of the curing agent, and improves the transparency of the curing agent. Since the IPDI reactivity is lower than that of MDI, in order to reduce the side reaction and shorten the reaction time, the polyester polyol is added dropwise.
  • the polyester polyol used for the polyurethane curing agent has a molecular weight controlled between 800 and 2000, has a large molecular weight, and reacts with the polyisocyanate monomer to form a polyurethane elastomer.
  • the hydroxyl value of the polyester polyol is controlled at 120-150 mg KOH/g, the hydroxyl value of the polyester polyol is large, the viscosity of the curing agent is small, and the NCO content is favorable, the hydroxyl group is low, and the polymerization degree (molecular weight) of the polyester polyol is larger.
  • the acid value of the polyester polyol is controlled to be 0.3 to 1.0 mgKOH/g, and the acid value cannot be less than 0.2 mgKOH/g. Otherwise, the reaction rate is too fast to control, and it is preferably controlled at 0.3 to 0.6 mgKOH/g.
  • the present invention relates to a method for preparing a scratch-resistant TDI and IPDI multi-polymer polyurethane curing agent, comprising the following components: low molecular weight polyester polyol 25 ⁇ 40%, diphenylmethane diisocyanate 15-40%, isophorone diisocyanate 12-25%, DBTL catalyst 0.05-0.3%, dimethyl carbonate 25-50%; the low molecular weight polyester polyol
  • the composition is: phthalic anhydride 10 to 25%, m- or terephthalic acid 10 to 25%, adipic acid or sebacic acid 3 to 8%, trimethylolpropane 7 to 15%, diol 25 to 45%, 2,6-di-tert-butyl-4-methylphenol 0.5 to 1.0%, Sb 2 O 3 /DBTL (3/1) catalyst 0.05 to 0.3%, dimethyl carbonate 5 to 12%; the diol It is one of propylene
  • the invention provides a preparation method of an anti-scratch MDI and IPDI multi-polymer polyurethane curing agent, comprising the following steps:
  • the preparation process is as follows: in the synthesis kettle, according to the formula amount, phthalic anhydride, m or terephthalic acid, adipic acid or azelaic acid, trimethylolpropane, binary Alcohol, 2,6-di-tert-butyl-4-methylphenol, Sb 2 O 3 /DBTL (3/1) catalyst, dimethyl carbonate, nitrogen gas for 10 minutes, the air in the kettle was removed, under the protection of nitrogen Heating and stirring; when the temperature of the kettle rises to about 180 °C, when the water starts to flow, the acid and hydroxyl value are sampled every 0.5h, and the temperature is raised to about 240 °C, and the temperature of the outlet water is controlled to 95-105 ° C.
  • the reaction time is 1.5 ⁇ 2h, the water output reaches more than 90% of the theoretical water output, and when it is basically constant, the esterification reaction ends; then, under normal pressure and nitrogen protection, the temperature is lowered to 180 °C, the nitrogen gas is stopped, and the vacuum is started, at 0.08 MPa. Vacuuming for 30min, pumping at 0.09MPa vacuum for 30min, then pumping at 0.095MPa vacuum for 1h, while heating to 240°C while vacuuming, sampling and measuring acid value and hydroxyl value. ;
  • the preparation process is as follows: in the synthesis kettle, MDI, IPDI and dimethyl carbonate are added according to the formula amount, and the temperature is raised to 50 ° C under stirring, and the solution is uniformly dissolved. After that, the low molecular weight polyester polyol in the step 1 is added dropwise, and the addition is completed in 1.5 to 2 hours; gradually, the temperature is gradually raised to 65 to 70 ° C, the DBTL catalyst is added, the reaction is maintained for 2 to 3 hours, and the temperature is lowered to 50 ° C in a vacuum.
  • the unreacted isocyanate monomer was removed for 1 h, cooled to 40 ° C, dimethyl carbonate was added to the solid content, and the solid content, viscosity, NCO and free isocyanate monomer values were sampled to obtain the desired discharge package.
  • the anti-scratch MDI and IPDI multipolymer polyurethane curing agent prepared by the invention has a solid content of 50-75%, an NCO content of 8-12%, a viscosity of 1200-2200 mPa ⁇ s, a free isocyanate ⁇ 1.0%, It does not contain aromatic hydrocarbons; it has the characteristics of environmental protection, good scratch resistance, good transparency and good yellowing resistance.
  • the polyurethane lacquer formulated with the hydroxy component has high gloss, high hardness, high transparency, good scratch resistance, good leveling, high fullness and good compatibility, and is used for wood, automobile, metal, Special curing agents such as plastics and other two-component polyester paints, polyurethane paints, decorative paints, matt paints, etc.
  • the acid and hydroxyl value are sampled every 0.5h when the water starts to be discharged, and the temperature is raised to about 240 °C. And control the outlet water temperature is 95 ⁇ 105 ° C, the reaction time is 1.5 ⁇ 2h, the water output reaches more than 90% of the theoretical water output, and when the amount is basically constant, the esterification reaction ends; then the temperature is lowered to 180 under normal pressure and nitrogen protection °C, stop the introduction of nitrogen, start vacuuming, pumping at 0.08MPa vacuum for 30min, pumping at 0.09MPa vacuum for 30min, then pumping at 0.095MPa vacuum for 1h, while heating to 240 °C while vacuuming,
  • the preparation process is as follows: in the synthesis kettle, 20 parts of diphenylmethane diisocyanate, 20 parts of isophorone diisocyanate and carbonic acid are added according to the formula amount. 25 parts of dimethyl ester, the temperature is raised to 50 ° C under stirring, and after dissolving uniformly, 35 parts of the low molecular weight polyester polyol in step 1 is added dropwise, and the addition is completed within 1.5 to 2 hours; gradually, the temperature is gradually raised to 65 to 70 ° C.
  • the performance of the anti-scratch MDI and IPDI multipolymer polyurethane curing agent prepared in this example was compared with that of the MDI/TMP, MDI/HDI, and IPDI trimer curing agents.
  • the preparation process is as follows: in the synthesis kettle, 25 parts of diphenylmethane diisocyanate, 15 parts of isophorone diisocyanate and carbonic acid are added according to the formula amount. 25 parts of dimethyl ester, the temperature is raised to 50 ° C under stirring, and after dissolving uniformly, 35 parts of the low molecular weight polyester polyol in step 1 is added dropwise, and the addition is completed within 1.5 to 2 hours; gradually, the temperature is gradually raised to 65 to 70 ° C.
  • the performance of the anti-scratch MDI and IPDI multipolymer polyurethane curing agent prepared in this example was compared with that of the MDI/TMP, MDI/HDI, and IPDI trimer curing agents.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明涉及一种抗划伤MDI及IPDI多聚物聚氨酯固化剂的制备方法，组分为：低分子量聚酯多元醇、MDI、IPDI、催化剂、碳酸二甲酯等，因聚酯多元醇含有芳环对称结构，具有刚性，提高了抗刮性、硬度和耐磨性；本发明制得的TDI及IPDI多聚物固化剂，固含量为50～75％，NCO含量为8～12％，粘度为1200～2200mPa·s、游离异氰酸酯≤1.0％、不含芳烃；具有环保、抗划伤好、透明性好、耐变黄性好等特点。与羟基组分配制的聚氨酯漆具有高光泽、高硬度、高透明性，漆膜抗划伤好、流平性好，丰满度高、相溶性好等特点，是用于木器、汽车、金属、塑料等各种双组分聚酯漆、聚氨酯漆、装饰漆、哑光漆等专用固化剂。

Description

一种抗划伤MDI及IPDI多聚物聚氨酯固化剂的制备方法 技术领域
本发明涉及一种聚氨酯固化剂的制备方法，尤其涉及到一种抗划伤MDI及IPDI多聚物聚氨酯固化剂。
背景技术
目前，市场上常用的多聚物聚氨酯固化剂为MDI/TMP、MDI/HDI、MDI/TDI产品中含有二甲苯和醋酸乙酯等有毒溶剂；固化剂含有一定量的游离单体HDI和MDI，它们是有毒化学品，化学性质非常活泼，挥发性高，具有强烈的刺激性气味和催泪作用，吸入后刺激呼吸系统，引起头痛支气管炎，严重的会导致死亡，并对环境造成严重污染。
IPDI异佛尔酮二异氰酸酯是一种脂环族异氰酸酯，IPDI反应活性比芳香族异氰酸酯低，但IPDI与羟基的反应速度比HDI与羟基的反应速度快4～5倍。由于二苯基甲烷二异氰酸酯MDI耐光性、耐黄变性较差，限制其用途，而异佛尔酮二异氰酸酯IPDI具有优异的光稳定性、耐共黄变性和耐化品性，但价格成本高。
发明内容
本发明旨在提供一种抗划伤MDI及IPDI多聚物聚氨酯固化剂的制备方法。
为了解决上面所述的技术问题，本发明采用二苯基甲烷二异氰酸酯MDI的经济性、低毒性和异佛尔酮二异氰酸酯IPDI性能优异性与低分子量聚酯多元醇反应制成MDI及IPDI多聚物聚氨酯固化剂；本发明中所用的低分子量聚酯多元醇采用苯酐、对苯二甲酸、间苯二甲酸或其衍生物与TMP、二元醇进行 酯化反应而成；用此聚酯多元醇制成的MDI及IPDI多聚物聚氨酯固化剂中的分子结构含有对称芳环结构，具有刚性，因而提高了抗刮性、硬度和耐磨性；添加适量的已二酸或癸二酸，改善固化剂成膜的柔韧性，降低了固化剂粘度，提高了固化剂的透明性。由于IPDI反应活性比MDI低，为了减少副反应，同时缩短反应时间，采用聚酯多元醇滴加方式进行。
用于聚氨酯固化剂的聚酯多元醇分子量控制在Mr 800～2000之间，分子量大，与多异氰酸酯单体反应易形成聚氨酯弹性体。聚酯多元醇的产品羟值控制在120～150mgKOH/g，聚酯多元醇羟值大，固化剂的粘度小，对提高NCO含量有利，羟基低，聚酯多元醇聚合度(分子量)越大，合成的固化剂粘度就越高，导致固化剂溶解性能变差；但羟基不能过高，否则固化剂成本也越高。聚酯多元醇的产品酸值控制在0.3～1.0mgKOH/g，酸值不能小于0.2mgKOH/g以下，否则反应速度太快难以控制，最好控制在0.3～0.6mgKOH/g。
由于二甲苯毒性大，大多数都不用二甲苯作合成中的回流溶剂，现在都用比较低毒的醋酸乙酯回流溶剂和兑稀溶剂，但醋酸乙酯还是毒性较大，沸点低(77℃)，易挥发用量大，做高固含聚氨酯固化剂溶解性差，粘度高，使用不方便；本发明采用环保的碳酸二甲酯作回流溶剂和兑稀溶剂，沸点高(90℃)，溶解性好，满足高固含聚氨酯固化剂的要求。
为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种抗划伤TDI及IPDI多聚物聚氨酯固化剂的制备方法，包括以下组分：低分子量聚酯多元醇25～40％、二苯基甲烷二异氰酸酯15～40％、异佛尔酮二异氰酸酯12～25％、DBTL催化剂0.05～0.3％、碳酸二甲酯25～50％；所述低分子量聚酯多元醇的组分是：苯酐10～25％、间或对苯二甲酸10～25％、已二酸或癸二酸3～8％、三羟甲基丙烷7～15％、二元醇25～45％、2，6-二叔丁基-4-甲基苯酚0.5～ 1.0％、Sb2O3/DBTL(3/1)催化剂0.05～0.3％、碳酸二甲酯5～12％；所述二元醇为丙二醇、二甘醇、新戊二醇的一种或其组合。
本发明提出一种抗划伤MDI及IPDI多聚物聚氨酯固化剂的制备方法，包括以下步骤：
1)、制备低分子量聚酯多元醇，其制备工艺如下：在合成釜中，按配方量依次加入苯酐、间或对苯二甲酸、已二酸或癸二酸、三羟甲基丙烷、二元醇、2，6-二叔丁基-4-甲基苯酚、Sb2O3/DBTL(3/1)催化剂、碳酸二甲酯，通入氮气10min，排除釜内的空气，在氮气保护下加热并搅拌；当釜温升至180℃左右时，开始出水时，每隔0.5h取样测定酸、羟值，继续升温至240℃左右保温，并控制出水温度为95～105℃，反应时间为1.5～2h，出水量达到理论出水量的90％以上，且基本恒定时，酯化反应结束；然后在常压及氮气保护下降温至180℃，停止通入氮气，开始抽真空，在0.08MPa真空度下抽30min、在0.09MPa真空度下抽30min、然后在0.095MPa真空度下抽1h，同时边抽真空边升温到240℃左右，取样测定酸值、羟值，达到要求后出料备用；
2)、制备抗划伤MDI及IPDI多聚物聚氨酯固化剂，其制备工艺如下：在合成釜中，按配方量加入MDI、IPDI和碳酸二甲酯，在搅拌下升温至50℃，溶解均匀后，滴加步骤1中的低分子量聚酯多元醇，在1.5～2h内滴加完毕；然逐步升温至65～70℃，加入DBTL催化剂，保持反应2～3h，降温到50℃，在真空下抽1h除去未反应的异氰酸酯单体，冷却到40℃，按固含量要求加入碳酸二甲酯兑稀，取样测定固含量、粘度、NCO和游离异氰酸酯单体值，达到要求后出料包装。
本发明制得的抗划伤MDI及IPDI多聚物聚氨酯固化剂，固含量为50～75％，NCO含量为8～12％，粘度为1200～2200mPa·s、游离异氰酸酯≤1.0％、 不含芳烃；具有环保、抗划伤好、透明性好、耐变黄性好等特点。与羟基组分配制的聚氨酯漆具有高光泽、高硬度、高透明性，漆膜抗划伤好、流平性好，丰满度高、相溶性好等特点，是用于木器、汽车、金属、塑料等各种双组分聚酯漆、聚氨酯漆、装饰漆、哑光漆等专用固化剂。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例1：
1)、低分子量聚酯多元醇的制备：在合成釜中，按配方重量比计，依次加入苯酐18份、间苯二甲酸13份、已二酸3.5份、三羟甲基丙烷11份、丙二醇15份、二甘醇30份、2，6-二叔丁基-4-甲基苯酚0.5份、Sb2O3/DBTL(3/1)催化剂0.1份，碳酸二甲酯8.9份，通入氮气10min，排除釜内的空气，在氮气保护下加热并搅拌；当釜温升至180℃左右时，开始出水时，每隔0.5h取样测定酸、羟值，继续升温至240℃左右保温，并控制出水温度为95～105℃，反应时间为1.5～2h，出水量达到理论出水量的90％以上，且基本恒定时，酯化反应结束；然后在常压及氮气保护下降温至180℃，停止通入氮气，开始抽真空，在0.08MPa真空度下抽30min、在0.09MPa真空度下抽30min、然后在0.095MPa真空度下抽1h，同时边抽真空边升温到240℃左右，取样经测定聚酯多元醇分子量为M r＝1000、酸值为0.5mgKOH/g、羟值为132mgKOH/g，符合技术要求出料备用；
2)、制备抗划伤MDI及IPDI多聚物聚氨酯固化剂，其制备工艺如下：在合成釜中，按配方量加入二苯基甲烷二异氰酸酯20份、异佛尔酮二异氰酸酯20份和碳酸二甲酯25份，在搅拌下升温至50℃，溶解均匀后，滴加步骤1中的低分子量聚酯多元醇35份，在1.5～2h内滴加完毕；然逐步升温至65～70℃， 加入DBTL催化剂0.09份，保持反应2～3h，降温到50℃，在真空下抽1h除去未反应的异氰酸酯单体，冷却到40℃，按固含量75±1％的要求加入碳酸二甲酯兑稀，取样测定TDI及IPDI多聚物聚氨酯固化剂固含量为75.5％、粘度为1560mPa·s、NCO为10.6％、游离异氰酸酯≤0.08％，产品符合技术要求后出料包装。
本实例制得的抗划伤MDI及IPDI多聚物聚氨酯固化剂与MDI/TMP、MDI/HDI、IPDI三聚体固化剂应用性能对比。
PU亮光漆A组分配方如下：60％亮光醇酸树脂60％、70％羟基丙烯酸树脂15％、60％醛酮树脂5％、流平剂0.2％、消泡剂0.2％、PU稀释剂19.6％；A组分∶75％固化剂B组分＝1∶0.7。
表1：配制的PU亮光漆性检测结果
Figure PCTCN2015080484-appb-000001
从表1看到，MDI及IPDI多聚物聚氨酯固化剂成膜后的性能在硬度、抗划伤性、耐磨性优于MDI/TMP、MDI/HDI、IPDI三聚体固化剂；在干燥 性、透明性和光泽上与MDI/TMP、MDI/HDI、IPDI三聚体固化剂相当；在耐黄变性与MDI/HDI相当，略差于IPDI三聚体，强优于MDI/TMP固化剂。
PU哑光漆A组分配方如下：60％哑光醇酸树脂60％、70％羟基丙烯酸树脂10％、消光粉5％、分散剂0.5％、防沉剂0.5％、流平剂0.3％、消泡剂0.2％、PU稀释剂24.0％；A组分∶75％固化剂B组分＝1∶0.5。
表2：配制的PU哑光漆性检测结果
Figure PCTCN2015080484-appb-000002
从表1看到，MDI及IPDI多聚物聚氨酯固化剂成膜后的性能在硬度、抗划伤性、耐磨性优于MDI/TMP、MDI/HDI、IPDI三聚体固化剂；在干燥性、透明性和光泽上与MDI/TMP、MDI/HDI、IPDI三聚体固化剂相当；在耐黄变性与MDI/HDI相当，略差于IPDI三聚体，强优于MDI/TMP固化剂。
实施例2：
1)、低分子量聚酯多元醇的制备：在合成釜中，按配方重量比计，依 次加入苯酐20份、对苯二甲酸12份、已二酸3份、三羟甲基丙烷10份、新戊二醇12份、二甘醇35份、2，6-二叔丁基-4-甲基苯酚0.5份、Sb2O3/DBTL(3/1)催化剂0.1份，碳酸二甲酯7.4份，通入氮气10min，排除釜内的空气，在氮气保护下加热并搅拌；当釜温升至180℃左右时，开始出水时，每隔0.5h取样测定酸、羟值，继续升温至240℃左右保温，并控制出水温度为95～105℃，反应时间为1.5～2h，出水量达到理论出水量的90％以上，且基本恒定时，酯化反应结束；然后在常压及氮气保护下降温至180℃，停止通入氮气，开始抽真空，在0.08MPa真空度下抽30min、在0.09MPa真空度下抽30min、然后在0.095MPa真空度下抽1h，同时边抽真空边升温到240℃左右，取样经测定聚酯多元醇分子量为M r＝1000、酸值为0.6mgKOH/g、羟值为135mgKOH/g，符合技术要求出料备用；
2)、制备抗划伤MDI及IPDI多聚物聚氨酯固化剂，其制备工艺如下：在合成釜中，按配方量加入二苯基甲烷二异氰酸酯25份、异佛尔酮二异氰酸酯15份和碳酸二甲酯25份，在搅拌下升温至50℃，溶解均匀后，滴加步骤1中的低分子量聚酯多元醇35份，在1.5～2h内滴加完毕；然逐步升温至65～70℃，加入DBTL催化剂0.08份，保持反应2～3h，降温到50℃，在真空下抽1h除去未反应的异氰酸酯单体，冷却到40℃，按固含量65±1％的要求加入碳酸二甲酯兑稀，取样测定TDI及IPDI多聚物聚氨酯固化剂固含量为75.2％、粘度为1680mPa·s、NCO为10.2％、游离异氰酸酯≤0.08％，产品符合技术要求后出料包装。
本实例制得的抗划伤MDI及IPDI多聚物聚氨酯固化剂与MDI/TMP、MDI/HDI、IPDI三聚体固化剂应用性能对比。
PU亮光漆A组分配方如下：60％亮光醇酸树脂60％、70％羟基丙烯酸树脂15％、60％醛酮树脂5％、流平剂0.2％、消泡剂0.2％、PU稀释剂19.6％； A组分∶75％固化剂B组分＝1∶0.7。
表3：配制的PU亮光漆性检测结果
Figure PCTCN2015080484-appb-000003
从表3看到，MDI及IPDI多聚物聚氨酯固化剂成膜后的性能在硬度、抗划伤性、耐磨性优于MDI/TMP、MDI/HDI、IPDI三聚体固化剂；在干燥性、透明性和光泽上与MDI/TMP、MDI/HDI、IPDI三聚体固化剂相当；在耐黄变性与MDI/HDI相当，略差于IPDI三聚体，强优于MDI/TMP固化剂。
PU哑光漆A组分配方如下：60％哑光醇酸树脂60％、70％羟基丙烯酸树脂10％、消光粉5％、分散剂0.5％、防沉剂0.5％、流平剂0.3％、消泡剂0.2％、PU稀释剂24.0％；A组分：75％固化剂B组分＝1∶0.5。
表4：配制的PU哑光漆性检测结果
Figure PCTCN2015080484-appb-000004
Figure PCTCN2015080484-appb-000005
从表1看到，MDI及IPDI多聚物聚氨酯固化剂成膜后的性能在硬度、抗划伤性、耐磨性优于MDI/TMP、MDI/HDI、IPDI三聚体固化剂；在干燥性、透明性和光泽上与MDI/TMP、MDI/HDI、IPDI三聚体固化剂相当；在耐黄变性与MDI/HDI相当，略差于IPDI三聚体，强优于MDI/TMP固化剂。
尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。

Claims (2)

  1. 一种抗划伤MDI及IPDI多聚物聚氨酯固化剂，其特征在于：包括以下组分：低分子量聚酯多元醇25～40％、二苯基甲烷二异氰酸酯15～40％、异佛尔酮二异氰酸酯12～25％、DBTL催化剂0.05～0.3％、碳酸二甲酯25～50％；所述低分子量聚酯多元醇的组分是：苯酐10～25％、间或对苯二甲酸10～25％、已二酸或癸二酸3～8％、三羟甲基丙烷7～15％、二元醇25～45％、2，6-二叔丁基-4-甲基苯酚0.5～1.0％、Sb2O3/DBTL(3/1)催化剂0.05～0.3％、碳酸二甲酯5～12％；所述二元醇为丙二醇、二甘醇、新戊二醇的一种或其组合。
  2. 一种如权利要求1所述的一种抗划伤MDI及IPDI多聚物聚氨酯固化剂的制备方法，其特征在于：所述制备方法，包括：
    1)、制备低分子量聚酯多元醇，其制备工艺如下：在合成釜中，按配方量依次加入苯酐、间或对苯二甲酸、已二酸或癸二酸、三羟甲基丙烷、二元醇、2，6-二叔丁基-4-甲基苯酚、Sb2O3/DBTL(3/1)催化剂、碳酸二甲酯，通入氮气10min，排除釜内的空气，在氮气保护下加热并搅拌；当釜温升至180℃左右时，开始出水时，每隔0.5h取样测定酸、羟值，继续升温至240℃左右保温，并控制出水温度为95～105℃，反应时间为1.5～2h，出水量达到理论出水量的90％以上，且基本恒定时，酯化反应结束；然后在常压及氮气保护下降温至180℃，停止通入氮气，开始抽真空，在0.08MPa真空度下抽30min、在0.09MPa真空度下抽30min、然后在0.095MPa真空度下抽1h，同时边抽真空边升温到240℃左右，取样测定酸值、羟值，达到要求后出料备用；
    2)、制备抗划伤MDI及IPDI多聚物聚氨酯固化剂工艺如下：在合成釜中，按配方量加入MDI、IPDI和碳酸二甲酯，在搅拌下升温至50℃，溶解均匀后，滴加步骤1中的低分子量聚酯多元醇，在1.5～2h内滴加完毕；然逐步升温至65～70℃，加入DBTL催化剂，保持反应2～3h，降温到50℃，在真空下抽1h 除去未反应的异氰酸酯单体，冷却到40℃，按固含量要求加入碳酸二甲酯兑稀，取样测定固含量、粘度、NCO和游离异氰酸酯单体值，达到要求后出料包装。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109320697A (zh) * 2018-09-19 2019-02-12 江苏三木化工股份有限公司 一种环保低毒水性饱和聚酯树脂及制备方法
CN113150240A (zh) * 2021-03-24 2021-07-23 北京小鸡磕技文化创意有限公司 一种环保型高硬度高透明聚氨酯树脂及其制备方法
CN113956427A (zh) * 2021-10-22 2022-01-21 东莞市米儿塑胶原料有限公司 永久型抗静电tpu的制备方法
CN114685755A (zh) * 2020-12-29 2022-07-01 浙江华峰新材料有限公司 一种耐养蒸聚氨酯弹性体及其制备方法
CN115181245A (zh) * 2022-08-16 2022-10-14 广东鼎立森新材料有限公司 一种hdi/ipdi固化剂、制备方法、用途及热固化pu胶膜
CN114149556B (zh) * 2021-11-18 2023-10-27 广东西顿新材料科技有限公司 一种醛酮改性自消光水性聚氨酯分散体及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591534A (zh) * 2019-10-11 2019-12-20 河北金达涂料有限公司 一种水性超薄耐候聚氨酯砂浆自流平涂料及其制备方法
CN111205432A (zh) * 2020-01-13 2020-05-29 上海稻畑精细化工有限公司 一种聚氨酯固化剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007015A1 (de) * 1990-10-11 1992-04-30 Henkel Kommanditgesellschaft Auf Aktien Feuchtigkeitshärtender schmelzkleber
CN103013325A (zh) * 2012-12-27 2013-04-03 合众（佛山）化工有限公司 一种抗划伤聚氨酯木器哑光黑面漆的制备方法
CN103045072A (zh) * 2012-12-27 2013-04-17 合众（佛山）化工有限公司 一种抗划伤耐黄变聚氨酯木器哑光白面漆的制备方法
CN103937401A (zh) * 2013-01-17 2014-07-23 合众（佛山）化工有限公司 一种抗划伤双组份聚氨酯木器亮光清漆的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3865080B2 (ja) * 1995-07-05 2007-01-10 東洋紡績株式会社 塗料用樹脂組成物
US20110201716A1 (en) * 2008-10-15 2011-08-18 Basf Se Polyester polyols based on terephthalic acid
AU2009333397A1 (en) * 2008-12-15 2010-07-08 E. I. Du Pont De Nemours And Company Copolyesters with enhanced tear strength
KR20140005283A (ko) * 2011-03-21 2014-01-14 바이엘 인텔렉쳐 프로퍼티 게엠베하 유기 공-용매가 필요하지 않은 수성 폴리에스테르-폴리우레탄 분산액
CN102268217B (zh) * 2011-06-09 2013-04-17 常州虹波涂料有限公司 直焊无焊渣聚氨酯漆包线漆的制备方法
CN102675578B (zh) * 2012-05-07 2013-11-13 上海交通大学 芳基聚酯聚氨酯树脂
CN102643407A (zh) * 2012-05-08 2012-08-22 上海东大聚氨酯有限公司 涂料固化用异佛尔酮二异氰酸酯预聚物的制备方法
CN103642009B (zh) * 2013-12-09 2016-03-09 山东一诺威聚氨酯股份有限公司 聚酯多元醇及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007015A1 (de) * 1990-10-11 1992-04-30 Henkel Kommanditgesellschaft Auf Aktien Feuchtigkeitshärtender schmelzkleber
CN103013325A (zh) * 2012-12-27 2013-04-03 合众（佛山）化工有限公司 一种抗划伤聚氨酯木器哑光黑面漆的制备方法
CN103045072A (zh) * 2012-12-27 2013-04-17 合众（佛山）化工有限公司 一种抗划伤耐黄变聚氨酯木器哑光白面漆的制备方法
CN103937401A (zh) * 2013-01-17 2014-07-23 合众（佛山）化工有限公司 一种抗划伤双组份聚氨酯木器亮光清漆的制备方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109320697A (zh) * 2018-09-19 2019-02-12 江苏三木化工股份有限公司 一种环保低毒水性饱和聚酯树脂及制备方法
CN114685755A (zh) * 2020-12-29 2022-07-01 浙江华峰新材料有限公司 一种耐养蒸聚氨酯弹性体及其制备方法
CN114685755B (zh) * 2020-12-29 2024-05-07 浙江华峰新材料有限公司 一种耐养蒸聚氨酯弹性体及其制备方法
CN113150240A (zh) * 2021-03-24 2021-07-23 北京小鸡磕技文化创意有限公司 一种环保型高硬度高透明聚氨酯树脂及其制备方法
CN113956427A (zh) * 2021-10-22 2022-01-21 东莞市米儿塑胶原料有限公司 永久型抗静电tpu的制备方法
CN114149556B (zh) * 2021-11-18 2023-10-27 广东西顿新材料科技有限公司 一种醛酮改性自消光水性聚氨酯分散体及其制备方法
CN115181245A (zh) * 2022-08-16 2022-10-14 广东鼎立森新材料有限公司 一种hdi/ipdi固化剂、制备方法、用途及热固化pu胶膜
CN115181245B (zh) * 2022-08-16 2024-03-15 广东鼎立森新材料有限公司 一种hdi/ipdi固化剂、制备方法、用途及热固化pu胶膜

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