CN109705339A - A kind of water-soluble multifunctional resin and preparation method thereof - Google Patents
A kind of water-soluble multifunctional resin and preparation method thereof Download PDFInfo
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- CN109705339A CN109705339A CN201711053102.XA CN201711053102A CN109705339A CN 109705339 A CN109705339 A CN 109705339A CN 201711053102 A CN201711053102 A CN 201711053102A CN 109705339 A CN109705339 A CN 109705339A
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- polyester amide
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Abstract
The present invention provides a kind of water-soluble multifunctional resin and its preparation method and application, the water-soluble multifunctional resin has the structure of following formula expression:Wherein, R HC=CH, R ' it is CH2CH(CH3) or (CH2CH2O)P, R " is (CH2)4Or the phenyl ring being connect with strand ortho position；X is that the residue after esterification occurs by one hydroxyl for plant polyatomic alcohol, and Y is that the residue after esterification occurs by its carboxyl for acrylic 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.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to one kind can not only be solidified with ultraviolet light but also can be with heat cure
Aqueous unsaturated carbamide resin of polyester amide and its preparation method and application.
Background technique
Photocuring (containing ultraviolet light, visible light, electron beam) material (containing coating, oil polish) is efficient, quick, energy saving, is to apply
The important directions that material, oil polish develop.Popular oiliness ultraviolet light solidification (UV) material is by oiliness UV resin, oil currently on the market
Property UV monomer, photoinitiator, diluent (organic solvent) composition, wherein in addition to oiliness UV resin, oiliness UV monomer all it is toxic simultaneously
Carcinogenic, diluent such as toluene etc. is toxic and is VOC ingredient, and waste of resource easily forms aerosol in conjunction 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
Word is counted show, China every year the death toll as caused by room air pollution up to 11.1 ten thousand people, be equivalent to it is national it is annual 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 entered stage of a Considering Environmental and the people's livelihood now, oil paint, oil polish due to its VOC discharge
It is caused haze, the wasting of resources, carcinogenic pathogenic, it is gradually abandoned by government and street levels, it is in all parts of the country to make in stringent limitation
With.If 2015 " Beijing Ambient pollution prevention ordinances " strictly limitation oil paint has used, other are such as Tianjin, Hebei, depth
Also Compulsory Feature with water paint has replaced oil paint on the ground such as ditch between fields, has assigned oil to oil paint manufacturing enterprise and has changed most later period of water
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
" about the notice for imposing the consumption tax to battery, coating " of publication in general bureau's on January 26th, 2015, will from 2 1st, 2015
Battery, coating are included in consumption tax range of collection, impose in production, consigned processing and import link, and being applicable in the tax rate is 4%, 2015
The consumption tax was postponed the imposition of a tax to lead storage battery before on December 31, in；From on January 1st, 2016, consumption is imposed by 4% tax rate to lead storage battery
Tax.It is lower than the coating exempt from consumption tax of 420 grams per liters (containing) to (VOC) content of volatile organic matter under Construction State.Industry scream
The autumn of Chinese coating industry has arrived.To avoid coatings industry from entering winter, has only and realize comprehensive aqueous of coating industry
Change to reduce or eliminate VOC emission.
The water paint of non-UV gradually attracts people's attention, but due to admittedly containing it is low, paint film is not full, glossiness is low, intolerant to
Water, difficult drying and forming-film, paint film intensity not enough, to add the reasons such as coalescing agent not environmentally that its application is made to receive limitation.Coating and
The developing direction of oil polish is Water-borne modification, UVization, is the optimal selection of replacement organic solvent because water is inexpensively environmentally friendly, and UVization
It is energy-efficient.The completely new not only UV solidification of exploitation again can heat cure multifunctional material system, elimination oiliness UV monomer, photoinitiator,
Organic diluent, heating adverse effect, replace oil paint system rapidly, it appears very urgent and necessary.Inventor is preceding
In phase research, unsaturated carbamide resin of polyester amide (CN1760234A, CN101293955A) is had developed, Ke Jiashui is deployed into aqueous
UV coating (a kind of performance study that Novel heating is coating material solidified, New Chemical Materials, volume 35, the 12nd phase, 11-13 pages,
2007).Water paint in view of using heat cure at present is also one of paint development direction, and exploitation both may be used on curing mode
Energy heat cure, multi-functional, excellent combination property unsaturated carbamide resin of polyester amide are taken seriously again for UV solidification.
Summary of the invention
The technical issues of solution: a kind of unsaturated polyester (UP) acyl is provided the purpose of the present invention is overcome the deficiencies in the prior art
Amine carbamide resin and its preparation method and application, the unsaturated carbamide resin of polyester amide not only take into account hardness and toughness, also have water
Dissolubility shows as multi-functional, uV curable and heat cure on curing mode, is widely used as preparing water-soluble multifunctional painting
The matrix resin of material.
Technical solution:
A kind of aqueous unsaturated carbamide resin of polyester amide, the structure indicated with following formula:
Wherein, R HC=CH, R ' it is CH2CH(CH3) or (CH2CH2O)P, R " is (CH2)4Or it is connect with strand ortho position
Phenyl ring；X is that the residue after esterification occurs by one hydroxyl for plant polyatomic alcohol, and Y is that acrylic 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.
The preparation method of the unsaturated carbamide resin of polyester amide is to mix binary acid, dihydric alcohol and urea, in nitrogen
After 200~600min is reacted in lower 160 DEG C~210 DEG C heating of gas shielded, distills and remove moisture removal, addition plant polyatomic alcohol, 160 DEG C~
60~120min are reacted in 210 DEG C of heating, add acrylic acid, and 60~120min are reacted in 80 DEG C~100 DEG C heating, cool down to get；
Wherein, binary acid, dihydric alcohol, urea molar ratio be 2: 1.0~1.8: 0.2~1.0；The quality of plant polyatomic alcohol and acrylic acid
Score is the 5%-8% of total amount.
Further, the binary acid is the mixture of binary acid A and binary acid B, mole of binary acid A and binary acid B
Than being 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 propylene glycol.
The unsaturated carbamide resin of polyester amide is preparing the application in multifunctional coating.
The utility model has the advantages that unsaturated carbamide resin of polyester amide of the invention introduces acrylic acid in the synthesis process, it is located at insatiable hunger
At the endpoint of carbamide resin of polyester amide strand, the conjugated degree of resin unsaturated group can be greatly improved, is increased substantially
Light sensitivity is made resin using photoinitiator, can be solidified with UV.Introduced plant polyalcohol in the synthesis process, compared with
More hydroxyls makes resin that can also make resin without using photoinitiator, can be solidified under heating conditions
Film, and can be reacted with such as carboxyl of the active function groups on substrate etc., adhesive force is improved, to effectively avoid using photoinitiator
The environmental pollution and personal injury that may cause.Using cheap raw materials such as urea and polyethylene glycol, in the water for having obtained resin
While dissolubility, cost is also reduced.Resin excellent combination property is widely used as preparing the matrix resin of multifunctional coating,
For the coating decoration of the substrates such as wood furniture floor, paper, plastics, metal and protection, there is very high application value.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of unsaturated carbamide resin of polyester amide of the invention.Ordinate unit is transmissivity
Transmittance, abscissa unit are wave number Wavenumbers:cm-1。
Specific embodiment
Embodiment 1
The synthesis of unsaturated carbamide resin of polyester amide:
0.1mol maleic anhydride, 0.1mol phthalic anhydride, 0.05mol urea and 0.15mol polyethylene glycol 400 are mixed,
It is fitted into the 250mL three-necked flask with water segregator, is placed in silicone oil bath, electric stirring, mixed 20 minutes at 100 DEG C.It is warming up to
150 DEG C, melt polymerization 40 minutes in nitrogen atmosphere, then 180 DEG C are warming up to, melt polymerization 120 minutes in nitrogen atmosphere, then be warming up to
It 200 DEG C, vacuumizes, melt polymerization in nitrogen atmosphere.Reaction water to be distillated reach theoretical amount 90% when, be added mass fraction account for
The plant polyatomic alcohol of upper monomer total amount 4%, 190 DEG C of heating react 60~120min, are cooled to 80 DEG C, add mass fraction and account for
The acrylic acid of the above monomer total amount 3%, 80 DEG C of heating react 60min, stop polymerization, be cooled to 50 DEG C and pour out, obtain after cooling
The liquid unsaturated carbamide resin of polyester amide of pale yellow transparent.
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, (1) 3534cm-1- N-H- feature the stretching vibration absworption peak at place, 1531cm-1Place occurs secondary
The II band of amide illustrates that polymerization reaction has occurred in urea and acid；(2)1720cm-1Locate the strong absorption band occurred, for stretching for C=O
Contracting vibration peak, 1271cm-1Place is C-O-C antisymmetric stretching vibration peak, the two peaks are all the characteristic peaks of ester；(3)1654cm-1
For the flexible peak of C=C key, 1461cm-1Place is=CH rocking vibration absorption peak, 987cm-1Place is then non-flat for trans-=CH
Rocking vibration absorption peak in face illustrates that the ester almost all of maleic anhydride during the reaction is isomerized to transconfiguration.Knot
Fruit shows that gained resin structure is consistent with theoretical value.
The water and 3% photoinitiator for accounting for resin quality 30% is added under room temperature in gained unsaturated carbamide resin of polyester amide
1173, film on a glass solidifies 5 minutes under 100WLED UV lamp after air-drying or is not added 150 degree of initiator and is heating and curing
30 minutes, the yield strength of gained film was 15.67MPa, breaking strength 13.76MPa, impact strength 68kg/cm.
Embodiment 2
The synthesis of unsaturated carbamide resin of polyester amide:
By 0.2mol maleic anhydride, 0.4mol adipic acid, 0.06mol urea and 0.3mol polyethylene glycol 400,
0.24mol mixed with propylene glycol is fitted into the 500mL three-necked flask with water segregator, 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 nitrogen atmosphere, then 180 DEG C are warming up to, melt polymerization in nitrogen atmosphere
120 minutes, then 200 DEG C are warming up to, it vacuumizes, melt polymerization in nitrogen atmosphere.Reaction water to be distillated reaches the 90% of theoretical amount
When, the plant polyatomic alcohol that mass fraction accounts for the above monomer total amount 3% is added, 190 DEG C of heating are reacted 60~120min, added
Mass fraction accounts for the acrylic acid of the above monomer total amount 4%, and 80 DEG C of heating react 60min, stop polymerization, be cooled to 50 DEG C and pour out,
The liquid unsaturated carbamide resin of polyester amide of pale yellow transparent 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 and 3% photoinitiator for accounting for resin quality 40% is added under room temperature in gained unsaturated carbamide resin of polyester amide
1173, film on a glass solidifies 5 minutes under 100WLED UV lamp after air-drying or is not added 150 degree of initiator and is heating and curing
30 minutes, the yield strength of gained film was 18.67MPa, breaking strength 12.74MPa, impact strength 69kg/cm.
Claims (5)
1. a kind of aqueous unsaturated carbamide resin of polyester amide, it is characterised in that: the structure indicated with following formula:
Wherein, R HC=CH, R ' it is CH2CH(CH3) or (CH2CH2O)P, R " is (CH2)4Or the benzene being connect with strand ortho position
Ring；X is that the residue after esterification occurs by one hydroxyl for plant polyatomic alcohol, and by its carboxyl ester occurs for Y for acrylic acid
Residue after changing reaction；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 aqueous unsaturated carbamide resin of polyester amide described in claim 1, it is characterised in that: by binary acid,
Dihydric alcohol and urea mixing, after 200~600min is reacted in 160 DEG C under nitrogen protection~210 DEG C heating, moisture removal is removed in distillation,
Plant polyatomic alcohol is added, 60~120min is reacted in 160 DEG C~210 DEG C heating, adds acrylic acid, and 80 DEG C~100 DEG C heating are anti-
Answer 60~120min, it is cooling to get；Wherein, binary acid, dihydric alcohol, urea molar ratio be 2: 1.0~1.8: 0.2~1.0；
The mass fraction of plant polyatomic alcohol and acrylic acid is the 5%-8% of total amount.
3. the preparation method of aqueous unsaturated carbamide resin of polyester amide according to claim 2, it is characterised in that: described two
The molar ratio of first sour mixture for binary acid A and binary acid B, binary acid A and binary acid B are 1: 0.4~2.5, and binary acid A is
Maleic 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 propylene glycol.
5. aqueous unsaturated carbamide resin of polyester amide described in claim 1 is water solubility, being applied to preparation both can be with ultraviolet light
Solidifying again can be with the water-soluble multifunctional coating of heat cure.
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| CN201711053102.XA CN109705339A (en) | 2017-10-26 | 2017-10-26 | A kind of water-soluble multifunctional resin and preparation method thereof |
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| CN201711053102.XA CN109705339A (en) | 2017-10-26 | 2017-10-26 | A kind of water-soluble multifunctional resin and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399706A (en) * | 1993-03-02 | 1995-03-21 | H. B. Fuller Licensing & Financing, Inc. | Imidazolidinone diamine and derivatives thereof |
| CN101293955A (en) * | 2007-04-26 | 2008-10-29 | 湖南大学 | Degradable unsaturated polyester amide urea copolymer and synthesizing method |
| CN105754091A (en) * | 2016-03-03 | 2016-07-13 | 江苏华夏制漆科技有限公司 | Unsaturated polyester-urea amide resin as well as preparation method and application thereof |
-
2017
- 2017-10-26 CN CN201711053102.XA patent/CN109705339A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399706A (en) * | 1993-03-02 | 1995-03-21 | H. B. Fuller Licensing & Financing, Inc. | Imidazolidinone diamine and derivatives thereof |
| CN101293955A (en) * | 2007-04-26 | 2008-10-29 | 湖南大学 | Degradable unsaturated polyester amide urea copolymer and synthesizing method |
| CN105754091A (en) * | 2016-03-03 | 2016-07-13 | 江苏华夏制漆科技有限公司 | Unsaturated polyester-urea amide resin as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 袁华 等: "一种具有自引发功能的紫外光固化低聚物的制备", 《应用化工》 * |
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Application publication date: 20190503 |