CN103193953B - Urethane acrylate with functionality of 12 as well as preparation method and application thereof - Google Patents
Urethane acrylate with functionality of 12 as well as preparation method and application thereof Download PDFInfo
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- CN103193953B CN103193953B CN201310085477.XA CN201310085477A CN103193953B CN 103193953 B CN103193953 B CN 103193953B CN 201310085477 A CN201310085477 A CN 201310085477A CN 103193953 B CN103193953 B CN 103193953B
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- citric acid
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Abstract
The invention belongs to the field of materials, and relates to urethane acrylate with functionality of 12 as well as a preparation method and application thereof. The urethane acrylate with functionality of 12 is prepared through the following steps of carrying out a reaction between anhydrous citric acid and ethylene oxide or epoxy propane under the action of a catalyst to obtain tetrahydroxy citric acid polyether ester, and carrying out a reaction between the tetrahydroxy citric acid polyether ester and diisocyanate and pentaerythritol tri(methyl)acrylate or di-trimethylolpropane tri(methyl)acrylate to obtain the urethane acrylate with functionality of 12. After being cured, the UV (Ultraviolet) photocureable urethane acrylate has the excellent properties of high hardness, wear resistance, scratch resistance, heat resistance, weather fastness and the like, and can be used as a raw material of UV coatings, printing ink and adhesives.
Description
Technical field
The invention belongs to Material Field, relate to a kind of 12 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 height, thereby be widely used in the fields such as coating, printing and electronic industry, development in recent years is rapid.Urethane acrylate (polyurethane acrylate, PUA) be a kind of important photocuring oligopolymer, there is the premium propertiess such as low stimulation, curing speed are fast, high transparent, stretch-proof, internal cohesive energy height, 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 12 functionality urethane acrylates are provided.
Another object of the present invention is to provide the preparation method of this 12 functionality urethane acrylate.
Another object of the present invention is to provide the application of this 12 functionality urethane acrylate.
Object of the present invention can be achieved through the following technical solutions:
A kind of 12 functionality urethane acrylates, prepare by the following method: the tetrahydroxy citric acid polyether ester first being made with oxyethane or propylene oxide reaction under catalyst action by Citric Acid, usp, Anhydrous Powder, tetrahydroxy citric acid polyether ester makes 12 functionality urethane acrylates with vulcabond and tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate reactions again.
Wherein,
The first step reaction scheme is as follows:
Work as n=2 ,-R is oxyethane and citric acid reactions during for-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, in autoclave, drip 5～8mol oxyethane or propylene oxide reaction in 155 DEG C～165 DEG C, reaction pressure is controlled at 0.2-0.6MPa, drip after oxyethane or propylene oxide 155 DEG C～165 DEG C and be incubated again 1～3 hour, then be cooled to below 80 DEG C, add atlapulgite to stir 30 minutes, the press filtration that circulates is until clear obtains tetrahydroxy citric acid polyether ester.
Described catalyzer is one or both or the 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.
12 functionality urethane acrylates of the present invention, preferably the prepared tetrahydroxy citric acid of 1mol polyether ester and 4～4.5mol vulcabond and 4～6mol tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate react and 12 functionality urethane acrylates described in making in 60 DEG C～95 DEG C.
12 functionality urethane acrylates of the present invention, further preferably 1mol prepared tetrahydroxy citric acid polyether ester and 4～4.5mol vulcabond are warmed up to 60 DEG C～65 DEG C stirring insulation reaction and within 2～3 hours, obtain intermediate formula (III) compound under the catalysis of catalyzer dibutyl tin laurate, intermediate formula (III) compound is at stopper, under the effect of catalyzer dibutyl tin laurate, be slowly warming up to 80 DEG C～85 DEG C insulation reaction in 0.5～1 hour with 4～6mol tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate and within 4～5 hours, make 12 functionality urethane acrylates.Wherein stopper can be MEHQ or Resorcinol, and its consumption is 100-5000ppm, and the each consumption of catalyzer dibutyl tin laurate 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 reacts to obtain 12 functionality urethane acrylates with pentaerythritol triacrylate:
The present invention's reaction that wherein the first step is prepared 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 reaction conditions of the present 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, be epoxy third (second) alkane complete reaction, transformation efficiency is more than 99.9%; What second step reaction was the isocyano in vulcabond and hydroxyl reacts, and belongs to known synthesis of polyurethane (polyurethane(s)) and reacts.
The preparation method of 12 functionality urethane acrylates of the present invention, prepare by the following method: the tetrahydroxy citric acid polyether ester first being made with oxyethane or propylene oxide reaction under catalyst action by Citric Acid, usp, Anhydrous Powder, tetrahydroxy citric acid polyether ester makes 12 functionality urethane acrylates (being formula (II) compound) with vulcabond and tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate reactions again.
Wherein, the preparation of tetrahydroxy citric acid polyether ester comprises the following steps: 1mol Citric Acid, usp, Anhydrous Powder is under catalyst action, in autoclave, drip 5～8mol oxyethane or propylene oxide reaction in 155 DEG C～165 DEG C, reaction pressure is controlled at 0.2-0.6MPa, drip after oxyethane or propylene oxide 155 DEG C～165 DEG C and be incubated again 1～3 hour, then be cooled to below 80 DEG C, add atlapulgite to stir 30 minutes, circulate press filtration until clear obtains tetrahydroxy citric acid polyether ester (formula (I)).
Described catalyzer is one or both or the 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 12 functionality urethane acrylates of the present invention, the prepared tetrahydroxy citric acid of 1mol polyether ester and 4～4.5mol vulcabond and 4～6mol tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate react and make 12 described functionality urethane acrylates in 60 DEG C～95 DEG C; One in the preferred TDI of described vulcabond, HDI, IPDI, HMDI, MDI.
The application of 12 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, need to adds phosphate aqueous solution and carry out neutralizing treatment, and then high vacuum dehydration, press filtration obtain polyether ester; The present invention adopts one or both or the two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, potassium benzoate, after polymerization is complete, do not need the acid adding neutralization that adds water, do not need high vacuum dehydration, 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 12 new functionality UV light-cured polyurethane acrylate and preparation method thereof.After this 12 functionality UV light-cured polyurethane acrylate solidifies, have that hardness is high, wear-resisting, scratch resistance, heat-resisting, weathering resistance etc. are good, can be in the raw material application as UV coating, ink, tackiness agent.
Embodiment
Embodiment 1:
In 6L autoclave, drop into 1920 grams of Citric Acid, usp, Anhydrous Powder (C
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, 155 DEG C～165 DEG C of temperature controls, pressure 0.10～0.40MPa, drips 3～4 hours, drips off rear 155 DEG C～165 DEG C insulations 2～3 hours, is then cooled to below 80 DEG C, discharging obtains crude product; Crude product adds 40 grams of atlapulgites to stir after 30 minutes, through the overanxious clear tetrahydroxy citric acid polyether ester (C that obtains
16h
28o
12, molecular weight 412) 4037.6 grams, structure as shown in the formula (I), wherein: n=2, a+b+c+d=5.
In 3000mL four-hole boiling flask, drop into tetrahydroxy citric acid polyether ester (C
16h
28o
12molecular weight 412) 206 grams, IPDI445 gram (2mol), 0.2 gram of catalyzer dibutyl tin laurate, be warmed up to 60 DEG C～65 DEG C and stir insulation reaction 2～3 hours, then add 1 gram of stopper MEHQ, 0.2 gram of catalyzer dibutyl tin laurate, 900 grams of pentaerythritol triacrylates, 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, make 12 functionality urethane acrylates, structure as shown in the formula (II), wherein:
R
1for:
n=2，a+b+c+d=5，
R
2for:
Embodiment 2:
In 6L autoclave, drop into 1920 grams of Citric Acid, usp, Anhydrous Powder (C
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, 155 DEG C～165 DEG C of temperature controls, pressure 0.10～0.40MPa, drips 3-4 hour, drips off rear 155 DEG C～165 DEG C insulation 2-3 hour, is then cooled to below 80 DEG C, discharging obtains crude product; Crude product adds 60 grams of atlapulgites to stir after 30 minutes, through the overanxious clear tetrahydroxy citric acid polyether ester (C that obtains
24h
44o
13, molecular weight 540) 5292 grams, structure as shown in the formula (I), wherein: n=3, a+b+c+d=6.
In 3000mL four-hole boiling flask, drop into tetrahydroxy polyether ester (C
24h
44o
13molecular weight 540) 270 grams, TDI350 gram, 0.2 gram of catalyzer dibutyl tin laurate, be warmed up to 60 DEG C～65 DEG C and stir insulation reaction 2～3 hours, then add 1 gram of MEHQ, 0.2 gram of catalyzer dibutyl tin laurate, 900 grams of pentaerythritol triacrylates, 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, make 12 functionality urethane acrylates, structure as shown in the formula (II), wherein:
R
1for:
n=3，a+b+c+d=6，
R
2for:
Embodiment 3
Starting material
12 functional group's aliphatic urethane acrylates prepared by UV resin: embodiment 1; Two functional group's aliphatic urethane acrylates (F5202, profit field, Jiangsu science and technology).
UV monomer: Viscoat 295 (TMPTA, profit field, Jiangsu); 1,6 hexanediol diacrylate (HDDA, profit field, Jiangsu); 2-phenoxyethyl acrylate (PHEA, 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 in mass ratio for 1:1:1 mixes.
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
The UV resin that takes certain mass, then adds UV monomer, light trigger, auxiliary agent, stirs, and is mixed with coating.The proportioning of coating is in Table l.
Table 1: the proportioning of coating
The preparation of film is with curing
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 μ m, on photo solidification machine, solidifies, and makes cured film reach surface drying, with referring to that touching dry method characterizes, and records set time.
Performance test
Set time: experiment adopts and refers to touch dry method, touches coating surface to point, and is clamminess if do not felt, thinks that coating surface is curing.
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 are the poorest.
Wear resistance: RCA test, 175g, 500 ± 50 times.
Water boiling resistance: with reference to standard GB/T/T1733 " paint film water tolerance assay method ".
Cold-hot circulation:
(1) scope and explanation: plastic paint is because of damp and hot circulation or losses of plasticizer, or both there will be the trend of cracking while having concurrently, adopt to be alternately exposed in climate cabinet and refrigerated tank and can measure the degree whether paint film ftractures 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 and be the hot case 24h of incubator of 38 DEG C.The placement of model should become with vertical direction 0-30 degree angle, and requires plate plate mutually not contact in process of the test.2. after 24h, immediately model is moved to 20h in the refrigerated tank of (23 ± 1.5) DEG C, should not exceed at most 30S transfer time.3. take out model, at room temperature place 4h, 48h is a circulation so altogether, can carry out during this time stage evaluation.4. carry out altogether 15 circulations, then model outward appearance, color, sticking power are tested.
(4) result represents: film should be without cracking, variable color, loss of adhesion or other defect.
(5) reference standard: USS AAMA615-02 " for industry standard, performance requriements and the test method of high-performance organic coating on plastic material ".
(1)
Result and discussion, the impact of resin on film performance
UV resin is the main body of UV coating, and its performance has determined to solidify the salient features of rear film substantially.This experiment adopts 12 functional group's aliphatic urethane acrylates and two functional group's aliphatic urethane acrylate resin composition different ingredients, and various composition consumptions are in table 1, and film performance is in table 2.
Table 2:12 official urethane acrylate and the impact of the different proportionings of two official's urethane acrylates on coating property
Reference:
(1) Yu Yingying. the method for inspection and instrument complete works for coatings industry. 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
CAS?NO：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 varnish of timber, metal, paper, plastics etc. etc.1173 special recommendations needs stand the UV-of long-term Exposure to Sunlight and resistance to xanthochromia coating material solidified in, owing to 1173 being liquid, be highly susceptible to blend, so be applicable to and the composite use of other light trigger, suggestion addition is 1-4%w/w.
Claims (6)
1. a functionality urethane acrylate, it is characterized in that preparing by the following method: the tetrahydroxy citric acid polyether ester first being made with oxyethane or propylene oxide reaction under catalyst action by Citric Acid, usp, Anhydrous Powder, tetrahydroxy citric acid polyether ester makes 12 functionality urethane acrylates with vulcabond and tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate reactions again; Wherein the preparation of tetrahydroxy citric acid polyether ester comprises the following steps: 1mol Citric Acid, usp, Anhydrous Powder is under catalyst action, in autoclave, drip 5 ~ 8mol oxyethane or propylene oxide reaction in 155 DEG C ~ 165 DEG C, reaction pressure is controlled at 0.2-0.6MPa, drip after oxyethane or propylene oxide 155 DEG C ~ 165 DEG C and be incubated again 1 ~ 3 hour, then be cooled to below 80 DEG C, add atlapulgite to stir 30 minutes, the press filtration that circulates is until clear obtains tetrahydroxy citric acid polyether ester; Described catalyzer is one or both or the 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. 12 functionality urethane acrylates according to claim 1, is characterized in that: the prepared tetrahydroxy citric acid of 1mol polyether ester and 4 ~ 4.5mol vulcabond and 4 ~ 6mol tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate react and make 12 described functionality urethane acrylates in 60 DEG C ~ 95 DEG C.
3. 12 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 12 functionality urethane acrylates claimed in claim 1, it is characterized in that: the tetrahydroxy citric acid polyether ester first being made with oxyethane or propylene oxide reaction under catalyst action by Citric Acid, usp, Anhydrous Powder, tetrahydroxy citric acid polyether ester makes 12 functionality urethane acrylates with vulcabond and tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate reactions again; Wherein the preparation of tetrahydroxy citric acid polyether ester comprises the following steps: 1mol Citric Acid, usp, Anhydrous Powder is under catalyst action, in autoclave, drip 5 ~ 8mol oxyethane or propylene oxide reaction in 155 DEG C ~ 165 DEG C, reaction pressure is controlled at 0.2-0.6MPa, drip after oxyethane or propylene oxide 155 DEG C ~ 165 DEG C and be incubated again 1 ~ 3 hour, then be cooled to below 80 DEG C, add atlapulgite to stir 30 minutes, the press filtration that circulates is until clear obtains tetrahydroxy citric acid polyether ester; Described catalyzer is one or both or the 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 12 functionality urethane acrylates according to claim 4, is characterized in that: the prepared tetrahydroxy citric acid of 1mol polyether ester and 4 ~ 4.5mol vulcabond and 4 ~ 6mol tetramethylolmethane three (methyl) acrylate or ditrimethylolpropane three (methyl) acrylate react and make 12 described functionality urethane acrylates in 60 DEG C ~ 95 DEG C; One in the preferred TDI of described vulcabond, HDI, IPDI, HMDI, MDI.
6. the application of 12 functionality urethane acrylates claimed in claim 1 in preparation UV coating, ink or tackiness agent.
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| 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 |
| CN110714336B (en) * | 2019-09-26 | 2022-08-05 | 江苏利田科技有限公司 | 9-functionality-degree PUA-based ultraviolet-curing coating adhesive for textile fabric and preparation method and application thereof |
| CN110699969B (en) * | 2019-09-26 | 2022-05-20 | 江苏利田科技股份有限公司 | Ultraviolet-curing coating adhesive for textile fabric based on polyfunctional polyurethane acrylate, and preparation method and application thereof |
| CN114957645B (en) * | 2022-05-23 | 2024-01-19 | 武汉中科先进材料科技有限公司 | Photo-curing super-hydrophilic coating composition for ABS (Acrylonitrile butadiene styrene) substrate and preparation method of coating of photo-curing super-hydrophilic coating composition |
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