CN1113918C - Synthesis of low-viscosity polyester-polyurethane acrylate resin - Google Patents

Synthesis of low-viscosity polyester-polyurethane acrylate resin Download PDF

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CN1113918C
CN1113918C CN 99126339 CN99126339A CN1113918C CN 1113918 C CN1113918 C CN 1113918C CN 99126339 CN99126339 CN 99126339 CN 99126339 A CN99126339 A CN 99126339A CN 1113918 C CN1113918 C CN 1113918C
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acid
polyester
weight percent
acrylate resin
polyurethane
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CN1299838A (en
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田禾
程翔
刘长路
张庆余
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

本发明属于低粘度聚酯聚氨酯丙烯酸酯树脂合成方法。该方法是用调聚缩聚酯化法合成出一端带有乙烯基、一端带有羟基的聚酯，然后加入异氰酸酯生成聚酯聚氨酯，最后用端羟基丙烯酸酯封端，形成不对称结构的聚酯聚氨酯丙烯酸酯树脂。本发明采用聚酯∶聚氨酯∶丙烯酸酯的摩尔比＝1.0∶1.0～1.1∶1.0～1.2。具有聚酯的低粘度、可流动、高韧性的优点，和有聚氨酯高耐磨、高强度的特点，同时两端还具有丙烯酸酯的高度感光性。The invention belongs to a method for synthesizing low-viscosity polyester polyurethane acrylate resin. The method is to synthesize a polyester with a vinyl group at one end and a hydroxyl group at one end by telomerization and polycondensation, then add isocyanate to generate polyester polyurethane, and finally end it with a hydroxyl-terminated acrylate to form a polyester with an asymmetric structure. Ester urethane acrylate resin. The present invention adopts the molar ratio of polyester: polyurethane: acrylate=1.0:1.0～1.1:1.0～1.2. It has the advantages of low viscosity, flowability and high toughness of polyester, and the characteristics of high wear resistance and high strength of polyurethane. At the same time, it also has the high sensitivity of acrylate at both ends.

Description

Synthesizing of low-viscosity polyester-polyurethane acrylate resin
The invention belongs to the low-viscosity polyester-polyurethane acrylate resin synthetic method.
Urethane resin because have high-wearing feature, tack, from extremely hard to extremely flexible adjustability, and have protectiveness and ornamental concurrently, so in radiation curing material, also be a kind that gains great popularity in very outstanding advantages such as one.But because the viscosity of urethane resin in the past is big, generally at room temperature be solid-state or semi-solid state, give and use and produce two aspects and all brought very big difficulty.And the price comparison height, be restricted so use.Chinese patent 97105247.6 discloses " synthetic method of photofixed polyester propenoic methyl carbamate ", and this method also provides a kind of low viscosity resin, and this resin is applicable to light-curable ink, because of its insufficient strength, and can not be as photo-cured coating and tackiness agent.
The synthetic method that the purpose of this invention is to provide a kind of low viscous polyester-polyurethane acrylate resin.This method is to synthesize an end and have the polyester that vinyl, an end have hydroxyl with telomerizing the polycondensation esterification process, the band aqua is toluene or benzene, add isocyanic ester then and generate polyester-polyurethane, use terminal hydroxy group vinylformic acid (methacrylic acid) ester class end-blocking at last, finally form the polyester-polyurethane acrylate resin of unsymmetrical structure.
In the unsymmetrical structure resin of the present invention, contain polyester, urethane, acrylate.Polyester portion invests material with lower viscosity and bigger snappiness, and the introducing of vinyl in the polyester is to have photosensitivity for an end that makes it.The adding of isocyanic ester, the reaction of an end of hydroxyl generates carbamate in one of them NCO and the polyester.After terminal hydroxy group vinylformic acid (methacrylic acid) ester class adds, another NCO reaction of one end of hydroxyl and isocyanic ester, also generate carbamate, invest the urethane performance of material with excellence, and terminal hydroxy group vinylformic acid (methacrylic acid) ester class, because an end has vinyl, makes the other end of resin also have photosensitivity.Formed like this polyester-polyurethane acrylate resin structure is asymmetric, promptly have polyester low viscosity, can flow, the advantage of high tenacity, have urethane high abrasion, high-intensity characteristics again, two ends also have the height photosensitivity of acrylate simultaneously.
The polyester that the present invention adopts: urethane: the mol ratio of acrylate=1.0: 1.0～1.1: 1.0～1.2.Its general structure is:
Figure C9912633900051
In the formula: the segment that the P-polyester diol forms.
The synthetic three-step reaction that divides carries out:
1. an end has polyester synthetic that vinyl, an end have hydroxyl.
With 1.0 moles acrylic or methacrylic acid, the diprotic acid of n mole (n＜8) specifically: adipic acid, sebacic acid, nonane diacid, sebacic anhydride, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, maleic acid etc.(n+1) Mo Er polyvalent alcohol, specifically: ethylene glycol, glycol ether, dipropylene glycol, 1,2 propylene glycol, 1,4 butyleneglycol, 1,6 hexylene glycol, neopentyl glycol, glycerol, TriMethylolPropane(TMP) etc.And the band aqua-benzene of total charging capacity (weight percent) 40-50% or toluene input reaction flask.Reaction flask is equipped with stirring, water-taker and condenser, ventilation bottom insert canal and thermometer etc.Add the catalyzer of (weight percent) 1.5-3.5% simultaneously, used catalyzer has: tetrabutyl titanate, titanium isopropylate, zinc acetate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, tosic acid, superpower solid acid etc.Drop into the stopper of (weight percent) 0.03-0.05%, used stopper has: Resorcinol, p methoxy phenol etc.Logical N 2Gas, stirring, intensification 80-110 ℃, the reaction times is 4-8 hour.When aquifer yield reach theoretical aquifer yield 97% the time finish.Last vacuum is taken off solvent, and the product that obtains is a polyester.
2. polyester-polyurethane is synthetic
With 1.0 moles polyester, drop into and be equipped with in the reaction flask of stirring, condenser, thermometer and ventpipe, add the catalyzer dibutyl tin laurate of (weight percent) 0.05% simultaneously, the stopper of (weight percent) 0.015-0.03%.Logical N 2Gas, stirring, intensification begin to drip 1.0～1.1 moles isocyanic ester in the time of 60 ℃, used isocyanic ester has: 1,6 hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), 65 ℃ of insulations 2-3 hour.
3. polyester-polyurethane acrylate resin is synthetic
After the reaction of second step is over, adjust temperature to 50～55 ℃, add (weight percent) 0.02-0.04% stopper, begin to drip the terminal hydroxy group acrylate of 1.0-1.2 mole, used terminal hydroxy group acrylate has: Hydroxyethyl acrylate, hydroxyethyl methylacrylate, 60 ℃ are incubated 1.5-2 hour, survey NCO≤0.5% o'clock end.The 40 ℃ of dischargings of lowering the temperature.
The range of viscosities that obtains resin is 8, and 000-3 can flow under the 5000CPS/25 ℃ of room temperature.
This low viscous urethane resin among the present invention, has over-all properties such as intensity preferably, can be in the application of printing ink, coating and tackiness agent, occupy higher ratio, overcoming the past haves no alternative but add the Macrodilution agent in order to reduce resin viscosity, thereby ensure that the said products has excellent specified property, has improved quality product.The urethane resin of this structure can be saved the consumption of 50% isocyanic ester, thereby has reduced the cost and the price of resin.
Embodiment provided by the invention is as follows:
Embodiment 1
1-1 on a 500mL there-necked flask, is equipped with stirring, water-taker and condenser.Drop into 1,2 glycol 93.5g, vinylformic acid 28.8g, benzene 140mL, catalyzer tosic acid (weight percent) 1.5%, stopper p methoxy phenol (weight percent) 0.05%.Heat up, stir.In stirring attitude, add hexanodioic acid 121.2g in the time of 40 ℃.Logical N 2Gas, reaction is carried out under solvent ebullient temperature.Reaction times is 5 hours, water outlet 37mL.Vacuum is taken off solvent, gets product 206.5g, and this product is transparent.
1-2 on a 500mL four-hole bottle, is equipped with stirring, has logical N in condenser, the thermowell 2Tracheae, and logical N 2Gas shiled.Drop into embodiment 1-1 products therefrom 155g, catalyzer dibutyl tin laurate (weight percent) 0.05%, stopper p methoxy phenol (weight percent) 0.03% heats up 60 ℃, drips hexamethylene vulcabond (HDI) 55.4g, and 65 ℃ are incubated 2 hours.
1-3 adjusts temperature to 55 ℃, adds p methoxy phenol (weight percent) 0.04%, drips propylene ester hydroxyl ethyl ester 41.8g, and 60 ℃ of insulations 1.5 hours are surveyed NCO≤0.5% and o'clock stopped.The 40 ℃ of dischargings of lowering the temperature get final product.
Embodiment 2
2-1 with example 1, in the device of 1-1, drops into glycol ether 47.3g, 1,2 propylene glycol 34g, vinylformic acid 18g, benzene 120mL, tosic acid (weight percent) 1.5%, p methoxy phenol (weight percent) 0.05%.Stir and heat up, in stirring, add hexanodioic acid 93.9g, logical N in the time of 40 ℃ 2Gas, reaction are to carry out under the solvent boiling temperature.5 hours reaction times, water outlet 27.6mL, vacuum is taken off solvent, can get transparent products 165g after the filtration.
2-2 with example 1, in the device of 1-2, leads to N 2Gas drops into embodiment 2-1 products therefrom 132.4g, catalyzer dibutyl tin laurate (weight percent) 0.05%, stopper p methoxy phenol (weight percent) 0.03%, heat up 60 ℃, drip isophorone diisocyanate (IPDI) 48.8g, 65 ℃ are incubated 2 hours.
2-3 adjusts temperature to 55 ℃, adds p methoxy phenol (weight percent) 0.04%, dropwise addition of acrylic acid hydroxyl ethyl ester 27.8g, and 60 ℃ of insulations 1.5 hours are surveyed NCO≤0.5% and o'clock are stopped.The 40 ℃ of dischargings of lowering the temperature.
Embodiment 3
3-1 with example 1, in the device of 1-1, drops into glycol ether 94.8g, vinylformic acid 14.4g, benzene 120mL, tosic acid (weight percent) 1.5%, and p methoxy phenol (weight percent) 0.05% stirs and heats up.In stirring, add hexanodioic acid 101.4g in the time of 40 ℃.Logical N 2Gas, reaction are to carry out under the solvent boiling temperature.In 4 hours reaction times, the last vacuum of water outlet 28.6mL is taken off solvent, can get transparent products 182g after the filtration.
3-2 with example 1, in the device of 1-2, feeds N 2Gas drops into embodiment 3-1 products therefrom 173g, catalyzer dibutyl tin laurate (weight percent) 0.05%, stopper p methoxy phenol (weight percent) 0.03%, heat up 60 ℃, drip isophorone diisocyanate 46.5g, 65 ℃ are incubated 2 hours.
3-3 adjusts temperature to 55 ℃, adds p methoxy phenol (weight percent) 0.04%, dropwise addition of acrylic acid hydroxyl ethyl ester 28.6g, and 60 ℃ of insulations 1.5% hour are surveyed NCO≤0.5% and o'clock are stopped.Cool to 40 ℃ of dischargings.
Embodiment 4
4-1 with example 1, in the device of 1-1, drops into ethylene glycol 29g, 1,2 propylene glycol 35.6g vinylformic acid 10.8g, toluene 120mL, tosic acid (weight percent) 1.5%, and p methoxy phenol (weight percent) 0.05% stirs and heats up.In stirring, add in the time of 40 ℃ hexanodioic acid 114.9.Logical N 2Gas, reaction are to carry out under the solvent boiling temperature.5 hours reaction times, water outlet 31mL, filtration, vacuum are taken off solvent, get product 159.3g.
4-2 with example 1, in the device of 1-2, feeds N 2Gas drops into embodiment 4-1 products therefrom 148.7g, catalyzer dibutyl tin laurate (weight percent) 0.05%, stopper p methoxy phenol (weight percent) 0.03%, heat up 60 ℃, drip isophorone diisocyanate (IPDI) 34.2g, 65 ℃ are incubated 2 hours.
4-3 adjusts temperature to 55 ℃, adds p methoxy phenol (weight percent) 0.04%, dropwise addition of acrylic acid hydroxyl ethyl ester 21.1g, and 60 ℃ of insulations 1.5 hours are surveyed NCO≤0.5% and o'clock are stopped the 40 ℃ of dischargings of lowering the temperature.
Embodiment 5
5-1 with example 1, in the device of 1-1, drops into 1,4 butyleneglycol 44g, 1,2 propylene glycol 37.1g, vinylformic acid 10.8g, toluene 120mL, tosic acid (weight percent) 1.5%, p methoxy phenol (weight percent) 0.05%.Stir and heat up, in stirring, add Tetra hydro Phthalic anhydride 122.3g, logical N in the time of 40 ℃ 2Gas.Reaction is to carry out under the solvent boiling temperature.8 hours reaction times, water outlet 17.5mL, vacuum gets transparent products 196.7g after taking off solvent filter.
5-2 with example 1, in the device of 1-2, leads to N 2Gas drops into embodiment 5-1 products therefrom 183.4g, catalyzer dibutyl tin laurate (weight percent) 0.05%, stopper p methoxy phenol (weight percent) 0.03%, heat up 60 ℃, drip tolylene diisocyanate (TDI) 26.8g, 65 ℃ are incubated 2 hours.
5-3 adjusts temperature to 55 ℃, adds p methoxy phenol (weight percent) 0.04%, dropwise addition of acrylic acid hydroxyl ethyl ester 21.1g, and 60 ℃ of insulations 1.5 hours are surveyed NCO≤0.5% and o'clock are stopped.The 40 ℃ of dischargings of lowering the temperature.
This product can flow, but slightly＞3.5 ten thousand CPS/25 ℃ of viscosity, and color is dark during than aliphatic isocyanates.
Embodiment 6
6-1, this step repeats embodiment 3,3-1 fully
Get product 182g.
6-2 with example 1, in the device of 1-2, feeds N 2Gas, step products therefrom 173g on the input, catalyzer dibutyl tin laurate (weight percent) 0.05%, stopper p methoxy phenol (weight percent) 0.03% heats up 60 ℃, drips tolylene diisocyanate (TDI) 36.4g, and 65 ℃ are incubated 2 hours.
6-3 adjusts temperature to 55 ℃, adds p methoxy phenol (weight percent) 0.04%, dropwise addition of acrylic acid hydroxyl ethyl ester 28.6g, and 60 ℃ of insulations 1.5 hours are surveyed NCO≤0.5% and o'clock are stopped.The 40 ℃ of dischargings of lowering the temperature.
Embodiment 7
7-1 in the device of 1-1, drops into neopentyl glycol 72.1g, 1,2 propylene glycol 35.1g, vinylformic acid 14.4g, toluene 120mL, tosic acid (weight percent) 1.5%, p methoxy phenol (weight percent) 0.05% with example 1.Stir and heat up, in stirring, add hexanodioic acid 139.5g, logical N in the time of 40 ℃ 2Gas.Reaction is to carry out under the solvent boiling temperature.6 hours reaction times, the last vacuum of water outlet 38mL take off behind the solvent filter can with product 223.1g.
7-2 with example 1, in the device of 1-2, leads to N 2Gas.Drop into embodiment 7-1 products therefrom 167.4g catalyzer dibutyl tin laurate (weight percent) 0.05%, stopper p methoxy phenol (weight percent) 0.03% heats up 60 ℃, drips isophorone diisocyanate 36.6g, and 65 ℃ are incubated 2 hours.
7-3。Adjust temperature to 55 ℃, add p methoxy phenol (weight percent) 0.04%, dropwise addition of acrylic acid hydroxyl ethyl ester 21g, 60 ℃ of insulations 1.5 hours are surveyed NCO≤0.5% and o'clock are stopped.Be cooled to 40 ℃ of dischargings.
Embodiment 8
8-1 with example 1, in the device of 1-1, drops into glycol ether 92.7g, methacrylic acid 17.2g, and toluene 120ml, tosic acid (weight percent) 1.5%, Resorcinol (weight percent) 0.035% stirs and heats up.In the time of 40 ℃, in stirring, add hexanodioic acid 98.4g.Logical N 2Gas, reaction is carried out under the solvent boiling temperature.5 hours reaction times, water outlet 27.8ml.Vacuum is taken off solvent, can get product 180.4g after the filtration.
8-2 with example 1, in the device of 1-2, feeds N 2Gas drops into embodiment 8-1 products therefrom 180.4g, catalyzer dibutyl tin laurate (weight percent) 0.05%, and hydroquinone of polymerization retarder (weight percent) 0.02% heats up 60 ℃, drips hexamethylene vulcabond 37g, and 65 ℃ are incubated 2 hours.
8-3 adjusts temperature to 55 ℃, adds Resorcinol (weight percent) 0.025%, drips hydroxyethyl methylacrylate 31.2g, and 60 ℃ of insulations 2 hours are surveyed NCO≤0.5% and o'clock stopped the 40 ℃ of dischargings of lowering the temperature.

Claims (5)

1.一种低粘度聚酯聚氨酯丙烯酸酯树脂合成方法，其特征在于采用的聚酯∶聚氨酯∶丙烯酸酯的摩尔比＝1.0∶1.0～1.1∶1.0～1.21，合成分三步进行：1. a kind of synthetic method of low-viscosity polyester urethane acrylate resin, it is characterized in that the polyester that adopts: polyurethane: the mol ratio=1.0 of polyurethane: acrylate: 1.0～1.21 of 1.0～1.21, synthesis divides three steps and carries out: 1)一端带有乙烯基、一端带有羟基的聚酯的合成1) Synthesis of polyester with a vinyl group at one end and a hydroxyl group at one end 将1.0摩尔的丙烯酸或甲基丙烯酸，n摩尔的二元酸(n＜8)具体是：己二酸、葵二酸、壬二酸、葵二酸酐、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸或顺丁烯二酸、(n+1)摩尔的多元醇，具体是：乙二醇、一缩二乙二醇、一缩二丙二醇、1，2丙二醇、1，4丁二醇、1，6己二醇、新戊二醇、丙三醇或三羟甲基丙烷及总投料量(重量百分比)40-50％的带水剂一苯或甲苯投入反应瓶，反应瓶装有搅拌、带水器和冷凝器、通气插底管及温度计，同时加入(重量百分比)1.5-3.5％的催化剂，所用的催化剂有：钛酸四丁酯、钛酸四异丙酯、酯酸鋅、三氧化锑、对甲苯磺酸或超强固体酸，投入(重量百分比)0.03-0.05％的阻聚剂，所用的阻聚剂有：对苯二酚或对甲氧基苯酚，通N2气、搅拌、升温80-110℃，反应时间为4-8小时，当出水量达到理论出水量的97％时结束，最后真空脱掉溶剂，得到的产物为聚酯；1.0 moles of acrylic acid or methacrylic acid, n moles of dibasic acids (n<8) are specifically: adipic acid, sebacic acid, azelaic acid, sebacic anhydride, phthalic anhydride, isophthalic acid , terephthalic acid or maleic acid, (n+1) moles of polyols, specifically: ethylene glycol, diethylene glycol, dipropylene glycol, 1,2 propylene glycol, 1,4 butane Diol, 1,6 hexanediol, neopentyl glycol, glycerol or trimethylolpropane and 40-50% water-carrying agent-benzene or toluene of the total charge (weight percentage) are put into the reaction bottle, and the reaction bottle is packed There are stirring, water tank and condenser, venting bottom pipe and thermometer, and at the same time, 1.5-3.5% catalyst is added (weight percentage). The catalysts used are: tetrabutyl titanate, tetraisopropyl titanate, ester acid Zinc, antimony trioxide, p-toluenesulfonic acid or super strong solid acid, drop into (weight percent) 0.03-0.05% polymerization inhibitor, used polymerization inhibitor has: hydroquinone or p-methoxyphenol, common N 2 gas, stirring, heating up to 80-110 ° C, the reaction time is 4-8 hours, when the water output reaches 97% of the theoretical water output, it ends, and finally the solvent is removed in vacuum, and the obtained product is polyester; 2)聚酯聚氨酯的合成将1.0摩尔的聚酯，投入装有搅拌、冷凝器、温度计和通气管的反应瓶内，同时加入(重量百分比)0.05％的催化剂二月桂酸二丁基锡，(重量百分比)0.015-0.03％的阻聚剂，通N2气、搅拌、升温，60℃时开始滴加1.0～1.1摩尔的异氰酸酯，所用的异氰酸酯有：1，6己二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)或甲苯二异氰酸酯(TDI)，65℃保温2-3小时；2) Synthesis of polyester polyurethane: 1.0 mole of polyester is put into the reaction flask equipped with stirring, condenser, thermometer and vent pipe, and 0.05% catalyst dibutyltin dilaurate is added (weight percent) simultaneously, (weight percent ) 0.015-0.03% polymerization inhibitor, pass N 2 gas, stir, heat up, and start to add 1.0-1.1 moles of isocyanate dropwise at 60°C. The isocyanates used are: 1,6-hexamethylene diisocyanate (HDI), Ketone diisocyanate (IPDI) or toluene diisocyanate (TDI), keep warm at 65°C for 2-3 hours; 3)聚酯聚氨酯丙烯酸酯树脂的合成3) Synthesis of polyester polyurethane acrylate resin 第二步反应完了之后，调整温度到50～55℃，加入(重量百分比)0.02-0.04％阻聚剂，开始滴加1.0-1.2摩尔的端羟基丙烯酸酯，所用的端羟基丙烯酸酯有：丙烯酸羟乙酯或甲基丙烯酸羟乙酯，60℃保温1.5-2小时，测NCO≤0.5％时结束，降温40℃出料。After the second step reaction, adjust the temperature to 50-55°C, add (weight percent) 0.02-0.04% polymerization inhibitor, and start to drop 1.0-1.2 moles of hydroxyl-terminated acrylates. The hydroxyl-terminated acrylates used include: acrylic acid Hydroxyethyl ester or hydroxyethyl methacrylate, heat at 60°C for 1.5-2 hours, end when NCO≤0.5% is measured, cool down to 40°C and discharge. 2.如权利要求1所述的低粘度聚酯聚氨酯丙烯酸酯树脂合成方法，其特征在于所采用的二元酸为己二酸或邻苯二甲酸酐。2. low-viscosity polyester urethane acrylate resin synthesis method as claimed in claim 1 is characterized in that the dibasic acid that adopts is adipic acid or phthalic anhydride. 3.如权利要求1所述的低粘度聚酯聚氨酯丙烯酸酯树脂合成方法，其特征在于所采用的多元醇为乙二醇、一缩二乙二醇、1，2丙二醇、1，4丁二醇或新戊二醇。3. the synthetic method of low-viscosity polyester urethane acrylate resin as claimed in claim 1, is characterized in that the polyvalent alcohol that adopts is ethylene glycol, diethylene glycol, 1,2 propylene glycol, 1,4 butanediol alcohol or neopentyl glycol. 4.如权利要求1所述的低粘度聚酯聚氨酯丙烯酸酯树脂合成方法，其特征在于所采用的催化剂为对甲苯磺酸或二月桂酸二丁基锡。4. low-viscosity polyester urethane acrylate resin synthetic method as claimed in claim 1 is characterized in that the catalyzer that adopts is p-toluenesulfonic acid or dibutyltin dilaurate. 5.如权利要求1所述的低粘度聚酯聚氨酯丙烯酸酯树脂合成方法，其特征在于所采用的阻聚剂为对苯二酚或对甲氧基苯酚。5. low-viscosity polyester urethane acrylate resin synthesis method as claimed in claim 1 is characterized in that the polymerization inhibitor that adopts is hydroquinone or p-methoxyphenol.
CN 99126339 1999-12-16 1999-12-16 Synthesis of low-viscosity polyester-polyurethane acrylate resin Expired - Fee Related CN1113918C (en)

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CN103289364A (en) * 2013-05-19 2013-09-11 南京师范大学 Electron beam(EB) curing resin bonding agent for diamond wire and preparation method of resin bonding agent
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