CN107602851A - A kind of water-based self-initiating On Visible Light Cured Resin and its preparation method and application - Google Patents
A kind of water-based self-initiating On Visible Light Cured Resin and its preparation method and application Download PDFInfo
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- CN107602851A CN107602851A CN201610539669.7A CN201610539669A CN107602851A CN 107602851 A CN107602851 A CN 107602851A CN 201610539669 A CN201610539669 A CN 201610539669A CN 107602851 A CN107602851 A CN 107602851A
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Abstract
The invention provides a kind of water-based self-initiating On Visible Light Cured Resin and its preparation method and application, the water-based self-initiating On Visible Light Cured Resin has the structure that following formula represents：Wherein, R HC=CH, R ' it is CH2CH(CH3) or (CH2CH2O)P, R " is (CH2)4Or the phenyl ring being connected with strand ortho position；X is that the residue after esterification occurs by its hydroxyl for pentaerythritol triallyl ether, and Y is that the residue after esterification occurs by its carboxyl for cinnamic acid；M/n=1/2.5~2.5/1, s/n=1/2.5~2.5/1, m/s=1/2.5~2.5/1, (m+s)/n=1/5~5/1, X/Y=1/5~5/1.Its preparation method is to mix binary acid, dihydric alcohol and urea; after 160 DEG C under nitrogen protection~210 DEG C 200~600min of heating response; moisture removal is removed in distillation; add pentaerythritol triallyl ether; 160 DEG C~210 DEG C 60~120min of heating response, add cinnamic acid, 160 DEG C~210 DEG C 60~120min of heating response; cooling, is produced.The unsaturated carbamide resin of polyester amide of the present invention not only has self-initiating, also has water solubility and visible-light curing, applied to preparing water-based self-initiating visible-light curing coating.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of unsaturated polyester (UP) of water-based self-initiating visible ray
Acid amides carbamide resin and its preparation method and application.
Background technology
Photocuring (containing ultraviolet light, visible ray, electron beam) material efficient, quick, energy-conservation (containing coating, oil polish), is to apply
Material, the important directions of oil polish development.Popular oiliness ultraviolet light solidifies (UV) material by oiliness UV resins, oil currently on the market
Property UV monomers, light trigger, diluent (organic solvent) composition, wherein in addition to oiliness UV resins, oiliness UV monomers all it is poisonous simultaneously
Carcinogenic, diluent such as toluene etc. is poisonous and is VOC compositions, waste of resource, easily combines to form aerosol with the dust in air, leads
Cause haze.European Union just forbade producing oil-based paints before 10 years, but China is also largely using oil-based paints, last year nearly 15,000,000
In the painting loading amount of ton or so, oil-based paints have 10,000,000 tons.Investigation system from Chinese interior decoration association environment measuring center
Count numerical monitor, China every year the death toll as caused by room air pollution up to 11.1 ten thousand people, it is annual equivalent to the whole nation because
The number of traffic death.The pernicious gas of paint volatilization is the second largest stealthy killer of the mankind in addition to vehicle exhaust.
Society has been enter into the stage of a Considering Environmental and the people's livelihood now, and oil paint, oil polish are due to its VOC discharge
It is caused haze, the wasting of resources, carcinogenic pathogenic, gradually abandoned by government and street levels, it is in all parts of the country to make in strict limitation
With.Such as 2015《Beijing Ambient pollution prevention ordinance》Strictly limit oil paint to use, other are such as Tianjin, Hebei, depth
Also Compulsory Feature has replaced oil paint with water paint on the ground such as ditch between fields, and the most later stage that oil changes water has been assigned to oil paint manufacturing enterprise
It was limited to for the end of the year 2016, otherwise forces to close the door without exception.Most of oil paint has been driven away at present.According to the Ministry of Finance, the national tax
General bureau's issue on January 26th, 2015《On imposing the notice of the consumption tax to battery, coating》, will from 2 1st, 2015
Battery, coating are included in consumption tax range of collection, are imposed in production, consigned processing and import link, and it is 4%, 2015 to be applicable the tax rate
The consumption tax was postponed the imposition of a tax to lead accumulator before on December 31, in；From 1 day January in 2016, consumption is imposed by 4% tax rate to lead accumulator
Tax.It is less than the coating exempt from consumption tax of 420 g/l (containing) to volatile organic matter under Construction State (VOC) content.Industry is cried out in alarm
The autumn of Chinese coating industry has arrived.To avoid coatings industry from entering winter, have only and realize comprehensive water-based of coating industry
Change to reduce or eliminate VOC emission.
Non- UV water paint gradually attracts people's attention, but due to admittedly containing low, paint film is not full, glossiness is low, intolerant to
Water, difficult drying and forming-film, paint film insufficient strength, the reasons such as coalescents not environmentally are added its application is received limitation.Coating and
The developing direction of oil polish is Water-borne modification, photocuring, is the optimal selection for replacing organic solvent because water is inexpensively environmentally friendly, and light
Solidify energy-efficient.The brand-new water-based self-initiating visible light solidifying material system of exploitation, eliminate oiliness UV monomers, light trigger,
The harmful effect of organic diluent, ultraviolet light is rapid to substitute oiliness UV systems, it appears very urgent and necessary.Inventor is preceding
In phase research, unsaturated carbamide resin of polyester amide (CN1760234A, CN101293955A) is have developed, Ke Jiashui is deployed into water-based
UV coating (a kind of performance study of new ultra-violet photocureable coating, New Chemical Materials, volume 35, the 12nd phase, 11-13 pages,
2007).But because presence will use light trigger, solidified using ultraviolet light, it is environmentally friendly not enough.Develop water-based self-initiating visible ray
Solidification, excellent combination property unsaturated carbamide resin of polyester amide is taken seriously.
The content of the invention
The technical problem of solution：The purpose of the present invention is overcome the deficiencies in the prior art and provides a kind of unsaturated polyester (UP) acyl
Amine carbamide resin and its preparation method and application, the unsaturated carbamide resin of polyester amide not only takes into account hardness and toughness, also with water
Dissolubility and photocurable, it is widely used as preparing the matrix resin of UV-curable waterborne coatings.
Technical scheme：
A kind of unsaturated carbamide resin of polyester amide, there is the structure that following formula represents：
Wherein, R HC=CH, R ' it is CH2CH(CH3) or (CH2CH2O)P, R " is (CH2)4Or it is connected with strand ortho position
Phenyl ring；X is that the residue after esterification occurs by its hydroxyl for pentaerythritol triallyl ether, and Y is that cinnamic acid passes through its carboxylic
Residue after esterification occurs for base；M/n=1/2.5~2.5/1, s/n=1/2.5~2.5/1, m/s=1/2.5~2.5/1,
(m+s)/n=1/5~5/1, X/Y=1/5~5/1.
The preparation method of described unsaturated carbamide resin of polyester amide, it is to mix binary acid, dihydric alcohol and urea, in nitrogen
After lower 160 DEG C~210 DEG C 200~600min of heating response of gas shielded, moisture removal is removed in distillation, adds pentaerythrite triallyl
Ether, 160 DEG C~210 DEG C 60~120min of heating response add cinnamic acid, and 160 DEG C~210 DEG C heating responses 60~
120min, cooling, is produced；Wherein, binary acid, dihydric alcohol, the mol ratio of urea are 2: 1.0~1.8: 0.2~1.0；Ji Wusi
The mass fraction of alcohol triallyl ether and cinnamic acid is the 5%-8% of total amount.
Further, the binary acid is mole of binary acid A and binary acid B mixture, binary acid A and binary acid B
Than for 1: 0.4~2.5, binary acid A is maleic anhydride or fumaric acid, and binary acid B is adipic acid or phthalic anhydride.
Further, the dihydric alcohol is polyethylene glycol or propane diols.
Application of the unsaturated carbamide resin of polyester amide in water-based self-initiating visible-light curing coating is prepared.
Beneficial effect：The unsaturated carbamide resin of polyester amide of the present invention is introduced containing big unsaturated group in building-up process
Pentaerythritol triallyl ether and cinnamic acid, at the end points of unsaturated carbamide resin of polyester amide strand, can significantly carry
The conjugated degree of high resin unsaturated group, increases substantially light sensitivity, makes resin in the case of without using light trigger,
It is curable film-forming under conditions of radiation of visible light, so as to effectively avoid environment caused by using light trigger and ultraviolet light possible
Pollution and personal injury.Using cheap raw materials such as urea and polyethylene glycol, make that resin obtained it is water miscible simultaneously, also drop
Low cost.Resin excellent combination property, it is widely used as preparing the matrix resin of water-based self-initiating visible-light curing coating, uses
In the application decoration of the base materials such as wood furniture floor, paper, plastics, metal and protection, there is very high application value.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the unsaturated carbamide resin of polyester amide of the present invention.
Embodiment
Embodiment 1
The synthesis of unsaturated carbamide resin of polyester amide：
0.1mol maleic anhydrides, 0.1mol phthalic anhydrides, 0.05mol urea and 0.15mol polyethylene glycol 400s are mixed,
It is fitted into the 250mL three-necked flasks with water knockout drum, is placed in silicone oil bath, electric stirring, is mixed 20 minutes at 100 DEG C.It is warming up to
150 DEG C, melt polymerization 40 minutes in blanket of nitrogen, then 180 DEG C are warming up to, melt polymerization 120 minutes in blanket of nitrogen, then be warming up to
200 DEG C, vacuumize, melt polymerization in blanket of nitrogen.Reaction water to be distillated reach theoretical amount 90% when, add mass fraction account for
The pentaerythritol triallyl ether of upper monomer total amount 4%, 190 DEG C of 60~120min of heating response, add mass fraction account for
The cinnamic acid of upper monomer total amount 3%, 190 DEG C of 60~120min of heating response, stop polymerization, be cooled to 150 DEG C and pour out, after cooling
Obtain the solid unsaturated carbamide resin of polyester amide of light brown clear.
Gained unsaturated carbamide resin of polyester amide is characterized with FT-IR, shows different monomers residue functional group
Characteristic absorption peak.As shown in figure 1 ,-N-H- feature the stretching vibration absworption peaks at (1) 3435cm-1, illustrate that urea is sent out with acid
Polymerisation is given birth to；(2) the strong absorption band occurred at 1721cm-1, it is C=O stretching vibration peak, is C- at 1256cm-1
O-C antisymmetric stretching vibrations peak, the two peaks are all the characteristic peaks of ester；(3) 1644cm-1 is the flexible peak of C=C keys,
It is=CH rocking vibration absworption peaks at 1453cm-1, is then trans=CH wagging vibration absworption peaks at 987cm-1；
(4) there are big C-H stretching vibration absworption peaks in 2932cm-1, reflect the presence of flexible chain.As a result show gained resin structure with
Theoretical value it is consistent.
The water for accounting for resin quality 30% is added under normal temperature in gained unsaturated carbamide resin of polyester amide, is applied on a glass
Film, solidify 5 minutes under 100WLED lamps after air-drying, the yield strength of gained film is 16.74MPa, and fracture strength is
10.64MPa, impact strength 71kg/cm.
Embodiment 2
The synthesis of unsaturated carbamide resin of polyester amide：
By 0.2mol maleic anhydrides, 0.4mol adipic acids, 0.06mol urea and 0.3mol polyethylene glycol 400s,
0.24mol mixed with propylene glycol, it is fitted into the 500mL three-necked flasks with water knockout drum, is placed in silicone oil bath, electric stirring, at 100 DEG C
Mixing 20 minutes.150 DEG C are warming up to, melt polymerization 40 minutes in blanket of nitrogen, then 180 DEG C are warming up to, melt polymerization in blanket of nitrogen
120 minutes, then 200 DEG C are warming up to, vacuumize, melt polymerization in blanket of nitrogen.Reaction water to be distillated reaches the 90% of theoretical amount
When, add mass fraction and account for the pentaerythritol triallyl ether of above monomer total amount 3%, 190 DEG C of heating responses 60~
120min, the cinnamic acid that mass fraction accounts for above monomer total amount 4% is added, 190 DEG C of 60~120min of heating response, is stopped poly-
Close, be cooled to 150 DEG C and pour out, the solid unsaturated carbamide resin of polyester amide of light brown clear is obtained after cooling.
Gained unsaturated carbamide resin of polyester amide is characterized with FT-IR, the results showed that gained resin structure and reason
By the consistent of value.
The water for accounting for resin quality 40% is added under normal temperature in gained unsaturated carbamide resin of polyester amide, is applied on a glass
Film, solidify 5 minutes under 100WLED lamps after air-drying, the yield strength of gained film is 17.53MPa, and fracture strength is
11.15MPa, impact strength 68kg/cm.
Claims (5)
- A kind of 1. unsaturated carbamide resin of polyester amide, it is characterised in that：The structure represented with following formula：Wherein, R HC=CH, R ' it is CH2CH(CH3) or (CH2CH2O)P, R " is (CH2)4Or the benzene being connected with strand ortho position Ring；X is that the residue after esterification occurs by its hydroxyl for pentaerythritol triallyl ether, and Y is that cinnamic acid is sent out by its carboxyl Residue after raw esterification；M/n=1/2.5~2.5/1, s/n=1/2.5~2.5/1, m/s=1/2.5~2.5/1, (m+ S)/n=1/5~5/1, X/Y=1/5~5/1.
- 2. the preparation method of the unsaturated carbamide resin of polyester amide described in claim 1, it is characterised in that：By binary acid, binary Alcohol and urea mix, and after 160 DEG C under nitrogen protection~210 DEG C 200~600min of heating response, moisture removal is removed in distillation, adds Pentaerythritol triallyl ether, 160 DEG C~210 DEG C 60~120min of heating response, cinnamic acid is added, 160 DEG C~210 DEG C add 60~120min of thermal response, cooling, is produced；Wherein, the mol ratio of binary acid, dihydric alcohol, urea for 2: 1.0~1.8: 0.2~ 1.0；The mass fraction of pentaerythritol triallyl ether and cinnamic acid is the 5%-8% of total amount.
- 3. the preparation method of unsaturated carbamide resin of polyester amide according to claim 2, it is characterised in that：The binary acid For binary acid A and binary acid B mixture, binary acid A and binary acid B mol ratio are 1: 0.4~2.5, and binary acid A is along fourth Enedioic acid acid anhydride or fumaric acid, binary acid B are adipic acid or phthalic anhydride.
- 4. the preparation method of unsaturated carbamide resin of polyester amide according to claim 2, it is characterised in that：The dihydric alcohol For polyethylene glycol or propane diols.
- 5. the unsaturated carbamide resin of polyester amide described in claim 1 is applied to prepare water-based self-initiating visible-light curing coating.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760234A (en) * | 2005-10-13 | 2006-04-19 | 郭文迅 | Degradable unsaturated carbamide resin of polyester amide, and synthetic method |
| CN101293955A (en) * | 2007-04-26 | 2008-10-29 | 湖南大学 | Degradable unsaturated polyester amide urea copolymer and synthesizing method |
| CN102702512A (en) * | 2012-06-25 | 2012-10-03 | 湖南工业大学 | Degradable saturated polyester amide urea as well as preparation method and application of degradable saturated polyester amide urea |
| CN102816516A (en) * | 2011-06-09 | 2012-12-12 | 郭文迅 | Ultraviolet light-cured hydrophilic coating and preparation method thereof |
-
2016
- 2016-07-11 CN CN201610539669.7A patent/CN107602851A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760234A (en) * | 2005-10-13 | 2006-04-19 | 郭文迅 | Degradable unsaturated carbamide resin of polyester amide, and synthetic method |
| CN101293955A (en) * | 2007-04-26 | 2008-10-29 | 湖南大学 | Degradable unsaturated polyester amide urea copolymer and synthesizing method |
| CN102816516A (en) * | 2011-06-09 | 2012-12-12 | 郭文迅 | Ultraviolet light-cured hydrophilic coating and preparation method thereof |
| CN102702512A (en) * | 2012-06-25 | 2012-10-03 | 湖南工业大学 | Degradable saturated polyester amide urea as well as preparation method and application of degradable saturated polyester amide urea |
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Application publication date: 20180119 |