CN105949457A - Flexible unsaturated polyester-urea amide resin and synthesis method thereof - Google Patents

Flexible unsaturated polyester-urea amide resin and synthesis method thereof Download PDF

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Publication number
CN105949457A
CN105949457A CN201610317400.4A CN201610317400A CN105949457A CN 105949457 A CN105949457 A CN 105949457A CN 201610317400 A CN201610317400 A CN 201610317400A CN 105949457 A CN105949457 A CN 105949457A
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China
Prior art keywords
acid
polyester amide
resin
urea
unsaturated
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CN201610317400.4A
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Chinese (zh)
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郭文迅
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Hunan University
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Hunan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/12—Polyester-amides

Abstract

The invention provides flexible unsaturated polyester-urea amide resin and a synthesis method thereof. A melt phase polycondensation method is adopted, unsaturated diacid (anhydride)(maleic anhydride or fumaric acid) and saturated long-carbon-chain diacid (brassylic acid or pentadecanedioic acid) with the odd number of carbon atoms are subjected to copolymerization with polyethylene glycol or polypropylene glycol and urea, and the flexible, water-soluble and photocurable unsaturated polyester-urea amide resin is prepared. The resin can be taken as matrix resin for preparation of water-based UV paint, and is used for painting decoration and protection of base materials such as wooden furniture floors, paper, plastics, metals and the like.

Description

Flexible unsaturated carbamide resin of polyester amide and synthetic method thereof
Technical field
The present invention relates to macromolecular material and the method for chemosynthesis ultraviolet light polymerization.Use unsaturated diacid (acid anhydride) (maleic anhydride or fumaric acid) and the saturated Long carbon chain diacid (tridecandioic acid or pentacosandioic acid) containing odd numbers of carbon atoms and Polyethylene Glycol or polypropylene glycol, carbamide copolymerization prepared flexibility, water solublity, photo curable unsaturated polyester amide urea matrix resin.This resinoid can prepare waterborne UV coating as matrix resin, and the application for base materials such as wood furniture floor, paper, plastics, metals is decorated and protection.The advantages such as this resinoid also has aqueous, environmental protective, cost relatively low.
Technical background
UV (ultraviolet light polymerization) material (containing coating, oil polish) is efficient, quick, energy-conservation, is coating, the important directions of oil polish development.The most popular oiliness UV material is made up of oiliness UV resin, oiliness UV monomer, light trigger, diluent (organic solvent), wherein outside oil removing UV resin, oiliness UV monomer is the most poisonous and carcinogenic, diluent such as toluene etc. are poisonous and be VOC composition, waste resource, easily the dust in air is combined formation aerosol, causes haze.European Union just forbade before 10 years producing oil-based paints, but China is also using oil-based paints in a large number, and in the painting loading amount of last year nearly about 15,000,000 tons, oil-based paints has 10,000,000 tons.From the investigation statistics numerical monitor at China interior decoration association environment measuring center, the death toll that China is caused by room air pollution every year has reached 11.1 ten thousand people, is equivalent to national every day because of the number of traffic death.The harmful gas of paint volatilization is the second largest stealthy killers (http://info.pf.hc360.com/2014/11/040921479005.shtml) of the mankind outside deaeration tail gas.Society has been enter into the stage of a Considering Environmental and the people's livelihood now.Haze that oil paint, oil polish cause due to the discharge of its VOC, the wasting of resources, carcinogenic pathogenic, the most gradually abandoned by government and street levels, in all parts of the country all strictly limiting use.The most strictly limit oil paint to use such as " the Beijing Ambient pollution prevention ordinances " of 2015, other replace oil paint such as ground Compulsory Features the most such as Tianjin, Hebei, Shenzhen with water paint, the deadline date that oil paint manufacturing enterprise has assigned oily modify-water was the end of the year 2016, otherwise forced without exception to close the door.The most major part oil paint is driven away." about to battery, the notice of the coating collection consumption tax " issued on January 26th, 2015 according to the Ministry of Finance, the State Tax Administration, from 1 day February in 2015, list battery, coating in consumption tax range of collection, impose at production, consigned processing and import link, the applicable tax rate is 4%, and within 2015, lead battery was postponed the imposition of a tax the consumption tax before 31 days by December；From 1 day January in 2016, lead battery is imposed the consumption tax by 4% tax rate.Volatile organic matter under Construction State (VOC) content is less than the coating exempt from consumption tax of 420 grams per liters (containing).Arrived the autumn of the Chinese coating industry of industry scream (http://www.drcnet.com.cn/eDRCnet.common.web/DocSummary.aspx？Leafid=3038&docid=3848478).For avoiding coatings industry to enter winter, have only and realize the omnibearing Water-borne modification of coating industry to reduce or to eliminate VOC emission.The water paint of non-UV gradually attracts people's attention, but due to admittedly containing low, paint film is the fullest, glossiness is low, drying and forming-film the most water-fast, difficult, paint film insufficient strength, will add the reasons such as coalescents not environmentally and make it apply to receive restriction.The developing direction of coating and oil polish is Water-borne modification, UVization, because the cheap environmental protection of water, is the optimum selection replacing organic solvent, and UVization is energy-efficient.Develop brand-new aqueous UV material system, eliminate oiliness UV monomer, light trigger, the harmful effect of diluent, replace rapidly oiliness UV system, it appears the most urgent and necessary.Inventor in early-stage Study, have developed unsaturated carbamide resin of polyester amide (patent of invention: Guo Wenxun, Lin Xian. degradable unsaturated carbamide resin of polyester amide and synthetic method thereof, granted patent ZL200510032248.7；Patent of invention: Guo Wenxun, Shi Zongli, Fang Min, Sun Xiao, Sun Xiangyue. degradable unsaturated polyester amide urea copolymer and synthetic method thereof, granted patent ZL200710034813.2), can add water and be deployed into waterborne UV coating (Sun Xiao, Shi Zongli, Guo Wenxun, Ai Yongping, Fang Min, the performance study of a kind of new ultra-violet photocureable coating, New Chemical Materials, volume 35, the 12nd phase, 11-13 page, 2007).But more owing to there is the urea bond of rigidity, short carbon chain, more crisp after material filming, require that the occasion that pliability is good, application are restricted in paper polish, aluminium alloy punch process etc..Exploitation pliability good, the unsaturated carbamide resin of polyester amide of excellent combination property comes into one's own.
Summary of the invention
The technical problem to be solved in the present invention is, the defect existed for prior art, unsaturated carbamide resin of polyester amide and the synthetic method thereof of a kind of flexibility are proposed, by introducing the flexible Long carbon chain diacid containing odd numbers of carbon atoms in resins synthesis, replace part rigidity short carbon chain diacid, and use the polypropylene glycol of flexibility to replace part rigidity short carbon chain glycol, synthesis obtains flexibility, water solublity, photo curable unsaturated carbamide resin of polyester amide, it is widely used as preparing the matrix resin of waterborne UV coating, for wood furniture floor, paper, plastics, the application decoration of the base materials such as metal and protection.
One of technical solution of the present invention is, the general structure of the unsaturated carbamide resin of polyester amide of described flexibility is:
In formula R be HC=CH, R ' be (CH2C(CH3)O)q、(CH2CH2O)POne in group, R " it is (CH2)11、(CH2)13One in group, q value is between 4～10, p value is between 4～20, m is the molal quantity of the chain link of maleic anhydride or fumaric acid binary alcohol esters, and n is the molal quantity of the chain link of maleic anhydride or fumaric acid carbamide polyester amide urea, and s is the molal quantity of the chain link of tridecandioic acid or pentacosandioic acid binary alcohol esters, 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.
The two of the technical solution of the present invention are, the step of the synthetic method of the unsaturated carbamide resin of polyester amide of described environmentally degradable is:
Maleic anhydride or fumaric acid, tridecandioic acid or pentacosandioic acid, Polyethylene Glycol or polypropylene glycol are mixed by certain mol proportion with carbamide, wherein binary acid, dihydroxylic alcohols, urea mol ratio are 2:1.8～1.0:0.2～1.0, and in binary acid, the mol ratio of maleic anhydride or fumaric acid and tridecandioic acid or pentacosandioic acid is 1/2.5～2.5/1.This mixture is loaded in the container of band water knockout drum; it is placed in silicone oil bath; nitrogen is protected; electric stirring; 160 DEG C of-210 DEG C of reacting by heating 200～600 minutes, distillate by-product moisture, pour out while hot; being cooled to 25 DEG C, synthesis obtains the yellowish unsaturated polyester amide urea transparent to dark brown viscous liquid or semisolid.
Hereinafter the present invention is made and further illustrating.
Unsaturated carbamide resin of polyester amide is because using the cheap raw materials such as carbamide, with low cost, and excellent combination property has the highest using value.In resins synthesis, introduce the flexible Long carbon chain diacid containing odd numbers of carbon atoms, replace part rigidity short carbon chain diacid, and use the polypropylene glycol of flexibility to replace part rigidity short carbon chain glycol, resin flexible toughness can be greatly improved.The atomic structure of carbon of odd number can reduce material crystalline degree, makes resin flexible toughness improve further, it is thus achieved that good impact strength.
The sign of the unsaturated carbamide resin of polyester amide of synthesis:
The unsaturated carbamide resin of polyester amide FT-IR of synthesis is characterized, and such FT-IR spectrogram is complex, demonstrates the characteristic absorption peak of different monomers residue functional group.Accompanying drawing 1 is the IR spectrogram (mol ratio: carbamide/maleic anhydride/tridecandioic acid/polypropylene glycol 400=1.0/3.0/1.0/3.0) of unsaturated carbamide resin of polyester amide, and vertical coordinate unit is absorbance T%, and abscissa unit is wave number cm-1。(1)3421cm-1-N-H-feature stretching vibration the absworption peak at place, illustrates that carbamide and acid there occurs polyreaction；(2)1712cm-1The strong absorption band that place occurs, for the stretching vibration peak of C=O, 1255cm-1Place is C-O-C antisymmetric stretching vibration peak, and these two peaks are all the characteristic peaks of ester；(3)1639cm-1For the flexible peak of C=C key, 1444cm-1Place is=CH rocking vibration absworption peak, 978cm-1Place is then trans=CH wagging vibration absworption peak.At 2921cm-1There are big C-H stretching vibration absworption peak, the existence of the flexible chain that reflection is long.Test result indicate that the structure of all synthetic polymers is consistent with theoretical expectation.
The unsaturated carbamide resin of polyester amide performance of the present invention:
1) curing performance
Unsaturated carbamide resin of polyester amide oligomer mobility when higher than 100 DEG C is preferable, and processing characteristics is good, it is easy to mix with water.Rich in undersaturated C=C key in this resinoid, use at normal temperatures light trigger 1173,184, a kind of coating that unsaturated carbamide resin of polyester amide can be caused to join in TPO cross-linking reaction under ultraviolet light, become the film that pliability is good.The dosage of light trigger is 1%-5%.
2) mechanical property
The unsaturated carbamide resin of polyester amide of synthesis, rich in the ester bond of polarity and amide-urea bond, gives the mechanical property that material is good.The pliability that unsaturated carbamide resin of polyester amide shows.After mixing water 30% such as the test print of the unsaturated carbamide resin of polyester amide of embodiment 1 synthesis, add the light trigger 1173 accounting for amount of resin 3%, lamp is away from 30 seconds crosslinking curings of 20cm, 1000W ultra violet lamp, the yield strength recorded is 11.3657MPa, fracture strength is 10.9901MPa, and impact strength is 75kg/cm.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram (mol ratio: carbamide/maleic anhydride/tridecandioic acid/polypropylene glycol 400=1.0/3.0/1.0/3.0) of unsaturated carbamide resin of polyester amide.
Detailed description of the invention
Embodiment 1: the synthesis of unsaturated carbamide resin of polyester amide:
9.80g maleic anhydride (0.10 mole), 24.40g tridecandioic acid (0.10 mole), 3.00g carbamide (0.05 mole) and 60.00g polypropylene glycol 400 (0.15 mole) are mixed, load in the 250ml there-necked flask of band water knockout drum, it is placed in silicone oil bath, electric stirring, reacts 20 minutes at 100 DEG C.It is warming up to 150 DEG C, melt polymerization 40 minutes in blanket of nitrogen, then it is warming up to 180 DEG C, melt polymerization 120 minutes in blanket of nitrogen, then it is warming up to 200 DEG C, and evacuation, melt polymerization in blanket of nitrogen.When reaction water to be distillated reaches the 90% of theoretical amount, 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.

Claims (3)

1. flexibility, water solublity, a photo curable unsaturated carbamide resin of polyester amide, is characterized in that, dividing of it Carbon-carbon double bonds, urea bond, amido link, ester bond and (the CH while of in minor structure2)11Or (CH2)13Long aliphatic chain base Group；
Use the Polyethylene Glycol in dihydroxylic alcohols or polypropylene glycol, tridecandioic acid, pentacosandioic acid, fumaric acid, Several for base stock in maleic anhydride, carbamide monomer, synthesis obtain flexibility, water solublity, can light The unsaturated carbamide resin of polyester amide of solidification；
The general structure of unsaturated polyester amide urea is:
In formula R be HC=CH, R ' be (CH2C(CH3)O)q、(CH2CH2O)POne in group, R " be (CH2)11、(CH2)13One in group, q value is between 4～10, and p value is between 4～20, and m is along fourth The molal quantity of the chain link of enedioic acid acid anhydride or fumaric acid binary alcohol esters, n is maleic anhydride or anti-fourth The molal quantity of the chain link of enedioic acid carbamide polyester amide urea, s is tridecandioic acid or pentacosandioic acid The molal quantity of the chain link of binary alcohol esters, 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.
2. the synthetic method of the unsaturated carbamide resin of polyester amide of claim 1, is characterized in that, the method is: By maleic anhydride or fumaric acid, tridecandioic acid or pentacosandioic acid, Polyethylene Glycol or poly-the third two Alcohol is mixed by certain mol proportion with carbamide, and wherein binary acid, dihydroxylic alcohols, urea mol ratio are 2:1.8～1.0:0.2～1.0, maleic anhydride or fumaric acid and tridecandioic acid or pentadecane in binary acid The mol ratio of diacid is 1/2.5～2.5/1.This mixture is loaded in the container of band water knockout drum, is placed in silicone oil bath, Nitrogen is protected, electric stirring, and 160 DEG C of-210 DEG C of reacting by heating 200～600 minutes distillate by-product moisture, Pouring out while hot, be cooled to 25 DEG C, synthesis obtains the yellowish insatiable hunger transparent to dark brown viscous liquid or semisolid And polyester amide urea.
The synthetic method of unsaturated carbamide resin of polyester amide the most according to claim 2, is characterized in that, insatiable hunger It is to add in unsaturated carbamide resin of polyester amide at normal temperatures with the UV curing method of carbamide resin of polyester amide Enter to account for the water of resin gross mass 5%-100%, add account for resin gross mass 0.5%-5% light trigger 1173 or 184 or TPO, and add account for resin gross mass 0.2%-1% silicone levelling agent BYK3510 or BYK349 or DEGO245,200 revs/min of high speed dispersion 20 minutes, it is deployed into the aquosity ultraviolet light of flexibility Coating material solidified, then use the method for roller coat to be coated on paper or plank or iron plate or the base material such as aluminium foil or plastics On, infrared except solidifying 5 seconds-60 seconds film forming after water under the uviol lamp that power is 8000-1000 watt.
CN201610317400.4A 2016-05-13 2016-05-13 Flexible unsaturated polyester-urea amide resin and synthesis method thereof Pending CN105949457A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
方敏 等: "改性不饱和聚酯酰胺脲紫外光固化涂料的性能研究", 《化工新型材料》 *

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Application publication date: 20160921