CN103242508B - A kind of 4 functionality urethane acrylates and its preparation method and application - Google Patents

A kind of 4 functionality urethane acrylates and its preparation method and application Download PDF

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CN103242508B
CN103242508B CN201310143167.9A CN201310143167A CN103242508B CN 103242508 B CN103242508 B CN 103242508B CN 201310143167 A CN201310143167 A CN 201310143167A CN 103242508 B CN103242508 B CN 103242508B
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citric acid
urethane acrylates
polyether ester
functionality urethane
oxyethane
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CN103242508A (en
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胡剑飞
张丽丽
马怀祥
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JIANGSU LITIAN TECHNOLOGY CO LTD
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JIANGSU LITIAN TECHNOLOGY Co Ltd
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Abstract

The invention belongs to Material Field, relate to a kind of 4 functionality urethane acrylates and its preparation method and application.This 4 functionality urethane acrylate, prepare by the following method: first by Citric Acid, usp, Anhydrous Powder under catalyst action with oxyethane or propylene oxide reaction and obtained tetrahydroxy citric acid polyether ester, tetrahydroxy citric acid polyether ester react with vulcabond and Hydroxyethyl acrylate or Propylene glycol monoacrylate and obtains 4 functionality urethane acrylates.After the solidification of this 4 functionality UV curable urethane acrylate, have that hardness is high, wear-resisting, scratch resistance, the premium properties such as heat-resisting, weathering resistance, can apply at the raw material as UV coating, ink, tackiness agent.

Description

A kind of 4 functionality urethane acrylates and its preparation method and application
Technical field
The invention belongs to Material Field, relate to a kind of 4 functionality urethane acrylates and its preparation method and application.
Background technology
Along with developing rapidly and the strict restriction of legislations of environmental protection to solvent of science and technology, UV photocuring macromolecular material is more and more subject to people's attention.UV photo-curing material have quick solidifying, energy consumption low, pollute less, the premium properties such as efficiency is high, be thus widely used in the fields such as coating, printing and electronic industry, development in recent years is rapid.Urethane acrylate (polyurethaneacrylate, PUA) be a kind of important Photocurable oligomers, the premium properties such as have that low stimulation, curing speed are fast, high transparent, stretch-proof, internal cohesive energy are high, be widely used in the fields such as light-curable ink, coating, tackiness agent, be widely used at the U.S., Japan, countries in Europe.In recent years, along with UV-curing technology is in the rise of China, novel photo-curing material is more and more wider as the raw material purposes of UV coating, ink, tackiness agent, and usage quantity is increasing year by year.
Summary of the invention
The object of the invention is the above-mentioned deficiency for prior art, a kind of 4 functionality urethane acrylates are provided.
Another object of the present invention is to provide the preparation method of this 4 functionality urethane acrylate.
Another object of the present invention is to provide the application of this 4 functionality urethane acrylate.
Object of the present invention realizes by following technical scheme:
A kind of 4 functionality urethane acrylates, prepare by the following method: first by Citric Acid, usp, Anhydrous Powder under catalyst action with oxyethane or propylene oxide reaction and obtained tetrahydroxy citric acid polyether ester, tetrahydroxy citric acid polyether ester react with vulcabond and Hydroxyethyl acrylate or Propylene glycol monoacrylate and obtains 4 functionality urethane acrylates.
Wherein,
The first step reaction scheme is as follows:
Working as n=2, is oxyethane and citric acid reactions when-R is-H; Work as n=3 ,-R is-CH 3time be propylene oxide and citric acid reactions; Wherein a+b+c+d=5 ~ 8.
The preparation of tetrahydroxy citric acid polyether ester comprises the following steps: 1mol Citric Acid, usp, Anhydrous Powder is under catalyst action, 5 ~ 8mol oxyethane or propylene oxide reaction is dripped in 155 DEG C ~ 165 DEG C in autoclave, reaction pressure controls at 0.2-0.6MPa, after dripping oxyethane or propylene oxide, 155 DEG C ~ 165 DEG C are incubated 1 ~ 3 hour again, then less than 80 DEG C are cooled to, add atlapulgite and stir 30 minutes, carry out circulation press filtration until clear, obtain tetrahydroxy citric acid polyether ester.
Described catalyzer is one or both or two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, potassium benzoate, and catalyst levels is the 1wt% ~ 5wt% of Citric Acid, usp, Anhydrous Powder and oxyethane or propylene oxide total mass.
Atlapulgite consumption is the 1wt% ~ 5wt% of Citric Acid, usp, Anhydrous Powder and oxyethane or propylene oxide total mass.
4 functionality urethane acrylates of the present invention, the tetrahydroxy citric acid polyether ester obtained by preferred 1mol and 4 ~ 4.5mol vulcabond and 4 ~ 6mol Hydroxyethyl acrylate or Propylene glycol monoacrylate react and obtained 4 described functionality urethane acrylates in 60 DEG C ~ 95 DEG C.
4 functionality urethane acrylates of the present invention, tetrahydroxy citric acid polyether ester further preferably obtained by 1mol and 4 ~ 4.5mol vulcabond be warmed up under the catalysis of catalyst dibutyltin dilaurylate 60 DEG C ~ 65 DEG C stir insulation reaction 2 ~ 3 hours must intermediate formula (III) compound, intermediate formula (III) compound is at stopper, 80 DEG C ~ 85 DEG C insulation reaction, 4 ~ 5 hours obtained 4 functionality urethane acrylates were slowly warming up to 4 ~ 6mol Hydroxyethyl acrylate or Propylene glycol monoacrylate in 0.5 ~ 1 hour under the effect of catalyst dibutyltin dilaurylate.Wherein stopper can be MEHQ or Resorcinol, and its consumption is 100-5000ppm, and each consumption of catalyst dibutyltin dilaurylate is 100-3000ppm.
Described vulcabond is selected from the one in TDI, HDI, IPDI, HMDI, MDI.
Second step reaction scheme is as follows:
Tetrahydroxy citric acid polyether ester and di-isocyanate reaction obtain intermediate:
Intermediate and Hydroxyethyl acrylate react to obtain 4 functionality urethane acrylates:
The present invention's reaction that wherein the first step prepares 4 Hydroxycitric acid polyether esters is the opening (anionoid polymerization) that 3 carboxyls in citric acid and 1 hydroxyl and epoxy third (second) alkane carry out, for known organic chemical reactions, under the conditions of the reaction according to the invention, epoxy third (second) alkane is gaseous state, continuously feeding is complete, then insulation reaction 1-3 hour, drops to constant to high pressure reacting kettle inner pressure, i.e. epoxy third (second) alkane complete reaction, transformation efficiency is more than 99.9%; Second step reacts the reaction for the isocyano in vulcabond and hydroxyl, belongs to known synthesis of polyurethane (polyurethane(s)) reaction.
The preparation method of 4 functionality urethane acrylates of the present invention, prepare by the following method: first by Citric Acid, usp, Anhydrous Powder under catalyst action with oxyethane or propylene oxide reaction and obtained tetrahydroxy citric acid polyether ester, tetrahydroxy citric acid polyether ester react with vulcabond and Hydroxyethyl acrylate or Propylene glycol monoacrylate and obtains 4 functionality urethane acrylates (i.e. formula (II) compound).
Wherein, the preparation of tetrahydroxy citric acid polyether ester comprises the following steps: 1mol Citric Acid, usp, Anhydrous Powder is under catalyst action, 5 ~ 8mol oxyethane or propylene oxide reaction is dripped in 155 DEG C ~ 165 DEG C in autoclave, reaction pressure controls at 0.2-0.6MPa, after dripping oxyethane or propylene oxide, 155 DEG C ~ 165 DEG C are incubated 1 ~ 3 hour again, then less than 80 DEG C are cooled to, add atlapulgite and stir 30 minutes, carry out circulation press filtration until clear, obtain tetrahydroxy citric acid polyether ester (formula (I)).
Described catalyzer is one or both or two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, potassium benzoate, and catalyst levels is the 0.5wt% ~ 3wt% of Citric Acid, usp, Anhydrous Powder and oxyethane or propylene oxide total mass.
The preparation method of 4 functionality urethane acrylates of the present invention, the tetrahydroxy citric acid polyether ester obtained by 1mol and 4 ~ 4.5mol vulcabond and 4 ~ 6mol Hydroxyethyl acrylate or Propylene glycol monoacrylate react and obtained 4 described functionality urethane acrylates in 60 DEG C ~ 95 DEG C; One in described vulcabond preferred TDI, HDI, IPDI, HMDI, MDI.
The application of 4 functionality urethane acrylates of the present invention in preparation UV coating, ink or tackiness agent.
Beneficial effect:
It is different from traditional method that the present invention prepares polyether ester used catalyst, and traditional method catalyzer used is sodium hydroxide, potassium hydroxide, after polyreaction is complete, needs to add phosphate aqueous solution and carries out neutralizing treatment, and then high vacuum dehydration, press filtration obtain polyether ester; The present invention adopts one or both or two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, potassium benzoate, after being polymerized, do not need acid adding to add water neutralization, do not need high vacuum to dewater, only need add atlapulgite overanxious, filter residue is through water-soluble, catalyst-solvent, filters out atlapulgite, and the aqueous solution of catalyzer is through evaporative crystallization, realize recycling, reaction process belongs to green catalysis and cleaner production.
The present invention discloses a kind of 4 functionality UV curable urethane acrylate newly and preparation method thereof.After the solidification of this 4 functionality UV curable urethane acrylate, have that hardness is high, wear-resisting, scratch resistance, heat-resisting, weathering resistance etc. be excellent, can apply at the raw material as UV coating, ink, tackiness agent.
Embodiment
Embodiment 1:
1920 grams of Citric Acid, usp, Anhydrous Powder (C are dropped in 6L autoclave 6h 8o 7, molecular weight 192), 40 grams of sodium formiates, are warming up to 155 DEG C, start to drip oxyethane (C 2h 4o, molecular weight 44) 2200 grams react, temperature control 155 DEG C ~ 165 DEG C, pressure 0.2 ~ 0.6MPa, drips 3 ~ 4 hours, and drip off rear 155 DEG C ~ 165 DEG C insulations 2 ~ 3 hours, be then cooled to less than 80 DEG C, discharging obtains crude product; Crude product adds atlapulgite 40 grams and stirs after 30 minutes, considers to obtain clear tetrahydroxy citric acid polyether ester (C through circulation pressure 16h 28o 12, molecular weight 412) 4037.6 grams, structure as shown in the formula (I), wherein: n=2, a+b+c+d=5.
Tetrahydroxy citric acid polyether ester (C is dropped in 3000mL four-hole boiling flask 16h 28o 12molecular weight 412) 206 grams, IPDI445 gram (2mol), catalyst dibutyltin dilaurylate 0.2 gram, be warmed up to 60 DEG C ~ 65 DEG C and stir insulation reaction 2 ~ 3 hours, then stopper MEHQ 1 gram is added, catalyst dibutyltin dilaurylate 0.2 gram, Hydroxyethyl acrylate 266 grams, within 0.5 ~ 1 hour, be slowly warming up to the discharging in 4 ~ 5 hours of 80 DEG C ~ 85 DEG C insulation reaction, obtained 4 functionality urethane acrylates, structure as shown in the formula (II), wherein:
R 1for:
Embodiment 2:
1920 grams of Citric Acid, usp, Anhydrous Powder (C are dropped in 6L autoclave 6h 8o 7, molecular weight 192), 60 grams of potassium formiates, are warming up to 155 DEG C, start to drip propylene oxide (C 3h 6o, molecular weight 58) 3480 grams react, temperature control 155 DEG C ~ 165 DEG C, pressure 0.20 ~ 0.40MPa, drips 3-4 hour, and drip off rear 155 DEG C ~ 165 DEG C insulation 2-3 hour, be then cooled to less than 80 DEG C, discharging obtains crude product; Crude product adds atlapulgite 60 grams and stirs after 30 minutes, considers to obtain clear tetrahydroxy citric acid polyether ester (C through circulation pressure 24h 44o 13, molecular weight 540) 5292 grams, structure as shown in the formula (I), wherein: n=3, a+b+c+d=6.
Tetrahydroxy polyether ester (C is dropped in 3000mL four-hole boiling flask 24h 44o 13, molecular weight 540) and 270 grams, TDI(tolylene diisocyanate, molecular weight 174) 350 grams, catalyst dibutyltin dilaurylate 0.2 gram, is warmed up to 60 DEG C ~ 65 DEG C and stirs insulation reaction 2 ~ 3 hours, then add MEHQ 1 gram, catalyst dibutyltin dilaurylate 0.2 gram, Hydroxyethyl acrylate 266 grams, is slowly warming up to the discharging in 4 ~ 5 hours of 80 DEG C ~ 85 DEG C insulation reaction for 0.5 ~ 1 hour, obtained 4 functionality urethane acrylates, structure as shown in the formula (II), wherein:
R 1for:
Embodiment 3
Starting material
UV resin: 4 functional group's aliphatic urethane acrylates prepared by embodiment 1; Two functional group's aliphatic urethane acrylates (F5202, profit field, Jiangsu science and technology).
UV monomer: double pentaerythritol methacrylate (DPHA, profit field, Jiangsu); 1,6 hexanediol diacrylate (HDDA, profit field, Jiangsu).
Light trigger: 1173, Nanjing Wa Li Chemical Industry Science Co., Ltd.
Auxiliary agent: Tego432, Tego92, German enlightening is high.
Mixed solvent: N-BUTYL ACETATE, toluene, mibk are 1:1:1 mixing in mass ratio.
Instrument and equipment
LT-1002 type uv cure machine, blue sky Te Deng Development Co., Ltd; QFZ type paint film adhesion determinator, Tianjin Ke Lian material-testing machine factory; RCA paper tape wear resistant instrument, Shanghai modern environment project institute; Water-bath; Cold cycling equipment.The preparation of coating
Take the UV resin of certain mass, then add UV monomer, light trigger, auxiliary agent, stir, be mixed with coating.The proportioning of coating is in Table l.
Table 1: the proportioning of coating
The preparation of film and solidification
Select the ABS plastic sheet material of 10cm × 10cm, first at its surface spraying one deck thermoplastic acrylic resin white primer, 60 DEG C of baking 3h, again at its surface spraying UV finish paint, coating thickness is about 20 μm, and photo solidification machine solidifies, and makes cured film reach surface drying, touch dry method with finger to characterize, record set time.
Performance test
Set time: experiment adopts finger to touch dry method, touching coating surface, being clamminess if do not felt, namely think that coating surface solidifies to point.
Pencil hardness: measure with reference to GB6739-86 film pencil hardness method.
Sticking power: measure with reference to GB/T1720-88 film adhesive assay method.Be divided into 7 grades, 1 grade of the best, 7 grades the poorest.
Wear resistance: RCA tests, 175g, 500 ± 50 times.
Water boiling resistance: with reference to standard GB/T/T1733 " paint film water tolerance assay method ".
Cold-hot circulates:
(1) scope and explanation: plastic paint because of moisture and hot ageing or losses of plasticizer, or there will be the trend of cracking when both have concurrently, adopts and is alternately exposed in climate cabinet and refrigerated tank the degree that can measure paint film and whether ftracture and ftracture.
(2) instrument: 1. damp heat box, 2. refrigerated tank, 3. color measurement instrument, 4. draws lattice device.
(3) measuring method: 1. test piece is put into relative temperature 100%, temperature is the hot case 24h of incubator of 38 DEG C.The placement of model should become 0-30 degree angle with vertical direction, and requires that plate plate is not in contact with each other mutually in process of the test.2., after 24h, immediately model is moved to 20h in the refrigerated tank of (-23 ± 1.5) DEG C, transfer time at most should more than 30S.3. take out model, at room temperature place 4h, 48h is a circulation so altogether, and period can carry out stage evaluation.4. carry out 15 circulations altogether, then model outward appearance, color, sticking power are tested.
(4) result represents: film should without cracking, variable color, loss of adhesion or other defect.
(5) reference standard: USS AAMA615-02 " on plastic material the industry standard of high-performance organic coating, performance requriements and test method ". (1)result and discussion, resin is on the impact of film performance
UV resin is the main body of UV coating, and its performance determines the salient features of the rear film of solidification substantially.This experiment employing 4 functional group's aliphatic urethane acrylate and two functional group's aliphatic urethane acrylate resins form different ingredients, and various Ingredient Amount is in table 1, and film performance is in table 2.
Table 2:4 functional polyurethane acrylate and two functional polyurethane acrylate different ratio are on the impact of coating property
Reference:
(1) Yu Yingying. the coatings industry method of inspection and instrument complete works. Beijing: Chemical Industry Press, 2007:525.
Attached light trigger 1173 illustrates:
Manufacturer: Nanjing Wa Li Chemical Industry Science Co., Ltd
Chemical name: 2-hydroxy-2-methyl-1-phenyl-1-acetone
English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one
CASNO：7473-98-5
Molecular formula: C10H12O
Molecular weight: 164.2
Chemical structural formula:
Technical indicator:
Outward appearance: colourless to light yellow transparent liquid
Purity: >=99.0%
Boiling point: 80-81 DEG C (degree Celsius)
Transmittance: 425nm >=99.0%; 500nm >=99.3%
Fugitive constituent :≤0.2%
Ash :≤0.10%
Application:
1173 are applicable to vinylformic acid photocuring varnish system, as the varnish etc. of timber, metal, paper, plastics etc.1173 special recommendations, in the UV-needing to stand chronic sun exposure and color inhibition is coating material solidified, because 1173 is liquid, are highly susceptible to blended, so be applicable to and the composite use of other light trigger, suggestion addition is 1-4%w/w.

Claims (7)

1. a functionality urethane acrylate, it is characterized in that preparing by the following method: first by Citric Acid, usp, Anhydrous Powder under catalyst action with oxyethane or propylene oxide reaction and obtained tetrahydroxy citric acid polyether ester, tetrahydroxy citric acid polyether ester react with vulcabond and Hydroxyethyl acrylate or Propylene glycol monoacrylate and obtains 4 functionality urethane acrylates; Wherein the preparation of tetrahydroxy citric acid polyether ester comprises the following steps: 1mol Citric Acid, usp, Anhydrous Powder is under catalyst action, 5 ~ 8mol oxyethane or propylene oxide reaction is dripped in 155 DEG C ~ 165 DEG C in autoclave, reaction pressure controls at 0.2-0.6MPa, after dripping oxyethane or propylene oxide, 155 DEG C ~ 165 DEG C are incubated 1 ~ 3 hour again, then less than 80 DEG C are cooled to, add atlapulgite and stir 30 minutes, carry out circulation press filtration until clear, obtain tetrahydroxy citric acid polyether ester; Described catalyzer is one or both or two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, potassium benzoate, and catalyst levels is the 0.5wt% ~ 3wt% of Citric Acid, usp, Anhydrous Powder and oxyethane or propylene oxide total mass.
2. 4 functionality urethane acrylates according to claim 1, is characterized in that: the tetrahydroxy citric acid polyether ester obtained by 1mol and 4 ~ 4.5mol vulcabond and 4 ~ 6mol Hydroxyethyl acrylate or Propylene glycol monoacrylate react and obtained 4 described functionality urethane acrylates in 60 DEG C ~ 95 DEG C.
3. 4 functionality urethane acrylates according to claim 1 and 2, is characterized in that: described vulcabond is selected from the one in TDI, HDI, IPDI, HMDI, MDI.
4. the preparation method of 4 functionality urethane acrylates according to claim 1, it is characterized in that: first by Citric Acid, usp, Anhydrous Powder under catalyst action with oxyethane or propylene oxide reaction and obtained tetrahydroxy citric acid polyether ester, tetrahydroxy citric acid polyether ester react with vulcabond and Hydroxyethyl acrylate or Propylene glycol monoacrylate and obtains 4 functionality urethane acrylates; Wherein the preparation of tetrahydroxy citric acid polyether ester comprises the following steps: 1mol Citric Acid, usp, Anhydrous Powder is under catalyst action, 5 ~ 8mol oxyethane or propylene oxide reaction is dripped in 155 DEG C ~ 165 DEG C in autoclave, reaction pressure controls at 0.2-0.6MPa, after dripping oxyethane or propylene oxide, 155 DEG C ~ 165 DEG C are incubated 1 ~ 3 hour again, then less than 80 DEG C are cooled to, add atlapulgite and stir 30 minutes, carry out circulation press filtration until clear, obtain tetrahydroxy citric acid polyether ester; Described catalyzer is one or both or two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, potassium benzoate, and catalyst levels is the 0.5wt% ~ 3wt% of Citric Acid, usp, Anhydrous Powder and oxyethane or propylene oxide total mass.
5. the preparation method of 4 functionality urethane acrylates according to claim 4, is characterized in that: the tetrahydroxy citric acid polyether ester obtained by 1mol and 4 ~ 4.5mol vulcabond and 4 ~ 6mol Hydroxyethyl acrylate or Propylene glycol monoacrylate react and obtained 4 described functionality urethane acrylates in 60 DEG C ~ 95 DEG C.
6. the preparation method of 4 functionality urethane acrylates according to claim 4, is characterized in that described vulcabond is selected from the one in TDI, HDI, IPDI, HMDI, MDI.
7. the application of 4 functionality urethane acrylates according to claim 1 in preparation UV coating, ink or tackiness agent.
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CN104004451B (en) * 2014-05-20 2017-01-18 江苏利田科技股份有限公司 Automotive UV (Ultraviolet) light-cured camouflage coating and preparation method thereof
CN105820063B (en) * 2016-04-15 2017-11-17 江苏利田科技股份有限公司 A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application
CN105884655B (en) * 2016-04-15 2017-11-21 江苏利田科技股份有限公司 A kind of 4 degree of functionality urethane acrylates based on double trimethylolpropane and its preparation method and application
CN105860028A (en) * 2016-04-15 2016-08-17 江苏利田科技股份有限公司 Tri-functionality urethane acrylate based on 2, 2-dimethylolpropionic acid/2, 2-dimethylolbutanoic acid and preparation method and application of tri-functionality urethane acrylate
CN112662304B (en) * 2020-11-30 2022-08-16 澳达树熊涂料(惠州)有限公司 Weather-resistant ultraviolet-cured solvent-free spraying open transparent primer and preparation method thereof
CN112646107B (en) * 2020-12-18 2022-11-22 联泓(江苏)新材料研究院有限公司 Water-based polyurethane acrylate resin and preparation method and composition thereof

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