CN101293955A - Degradable unsaturated polyester amide urea copolymer and synthesizing method - Google Patents
Degradable unsaturated polyester amide urea copolymer and synthesizing method Download PDFInfo
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- CN101293955A CN101293955A CNA2007100348132A CN200710034813A CN101293955A CN 101293955 A CN101293955 A CN 101293955A CN A2007100348132 A CNA2007100348132 A CN A2007100348132A CN 200710034813 A CN200710034813 A CN 200710034813A CN 101293955 A CN101293955 A CN 101293955A
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Abstract
The invention relates to a melt polycondensation method for the synthesis of unsaturated polyester amide urea resin from dipropylene glycol or neopentyl glycol or polyethylene glycol, transbutene dioic acid or maleic anhydride and urea as raw materials. The synthesized unsaturated polyester amide urea resin has the advantages of controllable degradation rate, no toxicity and low cost. The transbutene dioic acid or maleic anhydride can be partially replaced by benzene anhydride, isophthalic acid or adipic acid. The dipropylene glycol or neopentyl glycol or polyethylene glycol can be partially replaced by ethylene glycol or propylene glycol. The resin is used as matrix of fracture internal fixation material, tissue engineering scaffold, bone graft substitute, environment-friendly binder, environment-friendly glass-reinforced plastics, environment-friendly painting, disposable tableware, packaging material, shopping bag, garbage bag, pharmaceutical coating or capsule, pharmaceutical slow-/controlled-release material, agricultural mulch film, etc. furthermore, the resin is recoverable.
Description
Technical field
The present invention relates to chemosynthesis environment and biodegradable macromolecular material and method.Adopting several in the monomers such as dipropylene glycol, neopentyl glycol, polyoxyethylene glycol, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, urea be basic raw material, synthesizes to obtain adjustable, nontoxic, the lower-cost unsaturated carbamide resin of polyester amide of degradation rate.This resinoid can be used as the body material of the degradation material of disposable product, medical bone internal fixation material, tissue engineering bracket material, the interim surrogate of osseous tissue, medicine dressing or capsule, medicament slow release material, UV curable ink, ultraviolet light polymerization paper coating, environment-friendly type glass reinforced plastic, caking agent, environment-friendly type ultraviolet-curing or ambient cure coating.
Technical background
Existing photo-cured coating all need adopt the volatile linking agent of deleterious light trigger and small molecules, and environment is polluted.Solvent based coating distributes volatile organic matter (VOC) in air when drying and forming-film, thereby human ecological environment is caused serious harm, and forms waste.For this reason various countries' environmental regulation to organic volatile in the coating system (VOC) content carry out strictness restriction (Nobel K L, Waterborne polyurethanes, Progress on organic Coatings, 1997,32:131-136).The tradition photo-curing material is not suitable for the printing and the application of the wrapping material of food sanitation product owing to the reason of using poisonous initiator, also do not have a photocuring product to obtain the permission of FDA (Food and Drug Adminstration) (FDA) at present, thereby the application of photo-cured coating is restricted.Traditional glass-reinforced plastic material also has similar problem.China is global first furniture big producing country and food-processing industry big country, annual a large amount of furniture of outlet and deep-processed food.Yet the green trade technology barriers that developed country constructs China have seriously hindered the foreign exchange earning of furniture and deep-processed food, and coatings for furniture that one of the main reasons is to use and food packaging article coating small molecules toxic substance such as phthalate, vinylbenzene etc. exceed standard.Therefore develop environmental protection coating material nontoxic, that VOC free discharges, no small molecules is separated out, eliminate environmental pollution, the green trade technology barriers that breakthrough developed country constructs China are extremely urgent.The degradable biological medical material has poly(lactic acid), poly-acid anhydrides, polyamino acid or the like, the Application Areas such as cover of coincideing at surgical sewing thread, soft tissue implantation, bone internal fixation material, drug sustained release system, gi tract be applied (Tang Suyang, the mechanism of degradation of medical degradable material and application prospect.China's aesthetic medicine, 2000,9 (1): 50-51).The poor-performing that yet the cost that existing bio-medical material has is higher, have is restricted its application.
Applicant is once mainly based on cheap raw material urea, with itself and inexpensive monomer such as C2-C4 dibasic alcohol, FUMARIC ACID TECH GRADE or maleic anhydride, phthalic anhydride etc. syntheticly obtained that degradation rate is adjustable continuously, nontoxic, solvent-free, used water transfer rare, mechanical property good, lower-cost environment-friendly type unsaturated carbamide resin of polyester amide, and patent applied for.Patent name: degradable unsaturated carbamide resin of polyester amide and synthetic method thereof, application number 200510032248.7.Rarely seen this patent report of unsaturated carbamide resin of polyester amide there is no other people and sets foot in.After this patent application, by using new alcohols monomer, the structure of unsaturated carbamide resin of polyester amide has the change of matter, the synthetic method of unsaturated carbamide resin of polyester amide, curing have all had the raising of matter, and facilitated the lifting of resin on performance, as new synthetic unsaturated carbamide resin of polyester amide can be when no initiator exists crosslinking curing under the UV-irradiation, and have the self cure performance can be without linking agent.So the new patent of application is protected.This resinoid has potential using value at the degradation material of disposable product, medical bone internal fixation material, tissue engineering bracket material, the interim surrogate of osseous tissue, medicine dressing or numerous areas such as capsule, medicament slow release material, environment-friendly type ultraviolet-curing printing ink, environment-friendly type ultraviolet-curing paper coating, environment-friendly type glass reinforced plastic, environment-friendly type ultraviolet-curing or ambient cure coating.
Summary of the invention
The technical problem to be solved in the present invention is, defective at the prior art existence, a kind of environment and biodegradable unsaturated carbamide resin of polyester amide and synthetic method thereof are proposed, can synthesize with it that to obtain degradation rate adjustable, nontoxic, lower-cost unsaturated carbamide resin of polyester amide, it can be widely used as medical bone internal fixation material, tissue engineering bracket material, the interim surrogate of osseous tissue, drug coating or capsule, medicine slow (control) is released material, the environment-friendly type caking agent, environment-friendly type glass reinforced plastic, environment-friendly type coating, disposable tableware, wrapping material, shopping bag, refuse bag, flowerpot, the matrix resin of agricultural mulching etc.
One of technical solution of the present invention is that the constitutional features of described environment and biodegradable unsaturated carbamide resin of polyester amide is while carbon-carbon double bonds, urea key, amido linkage and ester bond in its molecule.
Two of technical solution of the present invention is; the step of the synthetic method of described environment and biodegradable unsaturated carbamide resin of polyester amide is: MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE, dipropylene glycol or neopentyl glycol or polyoxyethylene glycol are mixed by certain mol proportion with urea; pack into and be with in the container of water trap; place silicone oil bath; nitrogen protection; electronic stirring; the reacting by heating certain hour; distillate by product moisture; pour out while hot; be cooled to room temperature (25 ℃), synthetic obtain yellowish to dark-brown thickness liquid state or the transparent unsaturated polyester amide urea of semi-solid state.
Described MALEIC ANHYDRIDE of this synthetic method or FUMARIC ACID TECH GRADE: dipropylene glycol or neopentyl glycol or polyoxyethylene glycol: the mol ratio of urea is 2: 1.8～1.0: 0.2～1.0, temperature of reaction is 100～200 ℃, reaction times is 200～600 minutes, MALEIC ANHYDRIDE in the reactant and FUMARIC ACID TECH GRADE can be partly by hexanodioic acids, phthalic anhydride, a kind of replacement in the m-phthalic acid, MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE account for more than 30% of diacid (acid anhydride) total mole number, dipropylene glycol or neopentyl glycol or polyoxyethylene glycol can be partly by propylene glycol, a kind of replacement in the ethylene glycol, dipropylene glycol or neopentyl glycol or polyoxyethylene glycol account for more than 10% of glycol total mole number, and the molecular-weight average of polyoxyethylene glycol is between 200-800.
After the unsaturated carbamide resin of polyester amide preparation is finished; can add the trimethylolpropane allyl ether that accounts for unsaturated carbamide resin of polyester amide total mass 8%～30%; nitrogen protection in former synthesizer; electronic stirring; 120-170 ℃ was reacted 1-3 hour down, obtains the end capped unsaturated carbamide resin of polyester amide of trimethylolpropane allyl ether.
The curing of unsaturated carbamide resin of polyester amide is to use oxidation-reduction trigger systems such as dibenzoyl peroxide-xitix of 1% or methylethyl ketone peroxide-cobalt naphthenate at normal temperatures, the butyl acrylate linking agent that accounts for the vinyl acetate of total mass 20%～50% or account for the methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated carbamide resin of polyester amide crosslinked, or use at normal temperatures and made unsaturated carbamide resin of polyester amide crosslinked in ultraviolet radiation 1-30 minute, or use 1% dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, a kind of and resin alloy in the initiators such as isopropyl benzene hydroperoxide, heating made resin crosslinks in 5-30 minute under 80 ℃-200 ℃, or 180 ℃-230 ℃ following heating made resin crosslinks in 5-30 minute in air atmosphere, and resin solidifies because of molecular weight increases;
Unsaturated carbamide resin of polyester amide solidifies preceding available 5%～30% water dilution reduces system viscosity, favourable forming process, and the resin after the curing can continue heating under 180 ℃-230 ℃ in air atmosphere made state of cure raising, intensity increase in 1-6 hour.
Below the present invention made further specify.
Based on the preparation degradable resin should minimize cost, the consideration of novel, nontoxic, excellent combination property, inexpensive raw materials such as employing urea, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, phthalic anhydride, m-phthalic acid, hexanodioic acid, dipropylene glycol, neopentyl glycol, polyoxyethylene glycol have been designed, select relatively mild reaction conditions, synthetic prepared degradation rate adjustable, nontoxic, with recyclable utilization, the lower-cost unsaturated carbamide resin of polyester amide in back.This resinoid can be widely used as medical bone internal fixation material, tissue engineering bracket material, the interim surrogate of osseous tissue, environment-friendly type caking agent, environment-friendly type glass reinforced plastic, environment-friendly type coating, disposable tableware, wrapping material, shopping bag, refuse bag, flowerpot, capsule for medicine, medicine slow (control) and release the matrix resin of material, agricultural mulching etc., so very high using value is arranged.
The structural characterization of synthetic unsaturated carbamide resin of polyester amide:
The synthetic unsaturated carbamide resin of polyester amide all characterizes with FT-IR.Accompanying drawing 1 is the IR spectrogram (mol ratio: urea/MALEIC ANHYDRIDE/Tetra hydro Phthalic anhydride/ethylene glycol/dipropylene glycol=1.0/2.0/2.0/1.1/2.1) of unsaturated carbamide resin of polyester amide.Its charateristic avsorption band is: acid amides N-H (3484cm-1) stretching vibration charateristic avsorption band, at 1722cm-1 strong C=O (1724cm-1) stretching vibration charateristic avsorption band is arranged, C=C stretching vibration charateristic avsorption band is arranged at the 1383cm-1 place, C-O stretching vibration absorption peak is arranged at 1157cm-1.Experimental result shows the structure and theoretical expect consistent of all synthetic polymers.At 2981cm
-1C-H stretching vibration absorption peak is arranged.At 3207-3529cm
-1Wide-COOH the absorption peak at place shows that residual-COOH is arranged in the polymkeric substance, can participate in the curing reaction that molecular weight increases.Experimental result shows the structure and theoretical expect consistent of all synthetic polymers.
Unsaturated carbamide resin of polyester amide performance of the present invention:
1) curing performance
The curing of unsaturated carbamide resin of polyester amide is that the butyl acrylate linking agent that uses oxidation-reduction trigger systems such as dibenzoyl peroxide-xitix of 1% or methylethyl ketone peroxide-cobalt naphthenate at normal temperatures, accounts for the vinyl acetate of total mass 20%～50% or account for the methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated carbamide resin of polyester amide crosslinked; Or use at normal temperatures and made unsaturated carbamide resin of polyester amide crosslinked in ultraviolet radiation 1-30 minute; Or use a kind of and resin alloy in the initiators such as 1% dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, isopropyl benzene hydroperoxide, 80 ℃-200 ℃ down heating made resin crosslinks in 5-30 minute; Or 180 ℃-230 ℃ following heating made resin crosslinks in 5-30 minute in air atmosphere, and resin solidifies because of molecular weight increases;
Unsaturated carbamide resin of polyester amide solidifies preceding available 5%～30% water dilution reduces system viscosity, favourable forming process, and the resin after the curing can continue heating under 180 ℃-230 ℃ in air atmosphere made state of cure raising, intensity increase in 1-6 hour.
2) degradation property
Prepare cylindrical unsaturated polyester amide urea rod (φ 4mm, long 10mm) with homemade tetrafluoroethylene mould, excellent quality is about 150mg.The unsaturated polyester amide urea rod is placed the distilled water of 100mL, and (25 ℃) leave standstill and carry out degradation experiment under the room temperature.Experimental result and theoretical calculate show, in the distilled water, and the time of gained unsaturated polyester amide urea material degradation 80%, different with forming, do not wait from 1 month to 50 years time.In distilled water, unsaturated polyester amide urea material degradation speed is influenced greatly by urea content.Urea content is higher, and degradation rate is faster.Unsaturated polyester amide urea material degradation speed belongs to the pH dependency, and degradation rate is slow in acid solution, and degradation rate is fast in alkaline solution.Proof stick (long 5mm as embodiment 1 synthetic unsaturated carbamide resin of polyester amide, diameter 4mm) be that complete degradation time is 97 ± 4 minutes in 11 the alkaline solution under 25 ℃ in the pH value, in the pH value is that complete degradation time is 1325 ± 12 days in 7 the water, is that complete degradation time is 969 ± 13 days in 3 the acid solution in the pH value.Consider the adjustability of material degradation speed, such material is except the degradation material that can be used as disposable product, the mechanical property that material is good also is expected to as medical bone internal fixation material, tissue engineering bracket material, the interim surrogate of osseous tissue, medicine dressing or capsular body material it, and the material of difficult degradation is expected to as environment-friendly type caking agent, environment-friendly type glass reinforced plastic, environment-friendly type coating.
3) mechanical property
The synthetic unsaturated carbamide resin of polyester amide is rich in polar ester bond, urea key and amido linkage, gives material good mechanical property.The mechanical property of material is influenced greatly by condition of cure also.Solidification value height, set time are long, or the ultraviolet light polymerization rating of set is big, set time is long, and then the material degree of crosslinking is big, and is very strong, but toughness is relatively poor; Solidification value is lower, set time is shorter, and then the material degree of crosslinking is little, good toughness, but soft, hardness is not enough.So select suitable condition of cure, to obtain comprehensive mechanical property material preferably.Use initiator to cause when solidifying temperature and get 80 ℃-130 ℃ and be advisable, get heat-up time and be advisable in 5-30 minute.Ultraviolet lamp power is advisable with 500W-2000W during photocuring, and irradiation time was advisable with 15 seconds-10 minutes.Mix water 30% back interval 20cm, 1000W ultra violet lamp crosslinking curing in 58 second in air atmosphere as embodiment 3 synthetic unsaturated carbamide resin of polyester amide, the tensile strength that records is 132.1MPa, and breaking tenacity is 77.6MPa.
Description of drawings
Fig. 1 is the IR spectrogram (mol ratio: urea/MALEIC ANHYDRIDE/Tetra hydro Phthalic anhydride/ethylene glycol/dipropylene glycol=1.0/2.0/2.0/1.1/2.1) of unsaturated carbamide resin of polyester amide
Embodiment
Embodiment 1: one of synthetic method of unsaturated carbamide resin of polyester amide:
0.40 mole of MALEIC ANHYDRIDE, 0.1 mole of urea and 0.31 mole of neopentyl glycol are mixed, pack in the 250ml there-necked flask of being with water trap, place silicone oil bath, electronic stirring, 100 ℃ were reacted 20 minutes down.Be warming up to 150 ℃, melt polymerization is 40 minutes in the nitrogen atmosphere, is warming up to 180 ℃ again, and melt polymerization is 120 minutes in the nitrogen atmosphere, is warming up to 200 ℃ again, and melt polymerization is 30 minutes in the nitrogen atmosphere.Treat that the distilled reaction water reaches 80% o'clock of theoretical amount, stop polymerization, be cooled to 150 ℃ and pour out, obtain the transparent semi-solid unsaturated carbamide resin of polyester amide of light brown after the cooling.
Embodiment 2: two of the synthetic method of unsaturated carbamide resin of polyester amide:
0.20 mole of MALEIC ANHYDRIDE, 0.20 mole of Tetra hydro Phthalic anhydride, 0.1 mole of urea and 0.23 mole of dipropylene glycol, 0.10 mole of ethylene glycol are mixed, pack in the 250ml there-necked flask of being with water trap, place silicone oil bath, electronic stirring, 100 ℃ were reacted 20 minutes down.Be warming up to 150 ℃, melt polymerization is 40 minutes in the nitrogen atmosphere, is warming up to 180 ℃ again, and melt polymerization is 120 minutes in the nitrogen atmosphere, is warming up to 200 ℃ again, and melt polymerization is 60 minutes in the nitrogen atmosphere, and melt polymerization is 60 minutes under the 40pa.Treat that the distilled reaction water reaches 80% o'clock of theoretical amount, stop polymerization, be cooled to 150 ℃ and pour out, obtain faint yellow transparent semi-solid unsaturated carbamide resin of polyester amide after the cooling.
Embodiment 3: three of the synthetic method of unsaturated carbamide resin of polyester amide:
0.20 mole of MALEIC ANHYDRIDE, 0.20 mole of Tetra hydro Phthalic anhydride, 0.1 mole of urea and 0.20 mole of propylene glycol, 0.10 mole of polyoxyethylene glycol (400) are mixed, pack in the 250ml there-necked flask of being with water trap, place silicone oil bath, electronic stirring, 100 ℃ were reacted 20 minutes down.Be warming up to 150 ℃, melt polymerization is 40 minutes in the nitrogen atmosphere, be warming up to 180 ℃ again, melt polymerization is 120 minutes in the nitrogen atmosphere, is warming up to 200 ℃ again, and melt polymerization is 60 minutes in the nitrogen atmosphere, treat that the distilled reaction water reaches 80% o'clock of theoretical amount, stop polymerization, be cooled to 150 ℃ and pour out, obtain faint yellow transparent semi-solid unsaturated carbamide resin of polyester amide after the cooling.
Claims (6)
1, a class environment and biodegradable unsaturated carbamide resin of polyester amide is characterized in that, while carbon-carbon double bonds, urea key, amido linkage and ester bond in its molecular structure;
Adopting several in the monomers such as dipropylene glycol, neopentyl glycol, polyoxyethylene glycol, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, urea be basic raw material, synthesizes to obtain adjustable, nontoxic, the lower-cost unsaturated carbamide resin of polyester amide of degradation rate;
The general structure of unsaturated polyester amide urea is:
R is C=C in the formula, can be partly by phenyl ring, and (CH
2)
4Replace Deng group, R ' is CH
2C (CH
3)
2CH
2, CH (CH
3) OCH (CH
3), (CH
2CH
2O)
pA kind of Deng in the group, can part by (CH
2)
2, CH (CH
3) CH
2Replace Deng group, the p value is between 4～20, and m is the mole number of the chain link of diacid (acid anhydride)-binary alcohol esters, and n is the mole number of the chain link of diacid (acid anhydride)-urea polyester amide urea, m/n=1/5～5/1.
2, the synthetic method of the unsaturated carbamide resin of polyester amide of claim 1 is characterized in that, this method is:
MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE, dipropylene glycol or neopentyl glycol or polyoxyethylene glycol are mixed by certain mol proportion with urea; pack into and be with in the container of water trap; place silicone oil bath; nitrogen protection, electronic stirring, reacting by heating certain hour; distillate by product moisture; pour out while hot, be cooled to room temperature (25 ℃), synthetic obtain yellowish to dark-brown thickness liquid state or the transparent unsaturated polyester amide urea of semi-solid state.
3, synthetic method according to the described unsaturated carbamide resin of polyester amide of claim 2, it is characterized in that, described MALEIC ANHYDRIDE of synthetic method or FUMARIC ACID TECH GRADE: dipropylene glycol or neopentyl glycol or polyoxyethylene glycol: the mol ratio of urea is 2: 1.8～1.0: 0.2～1.0, temperature of reaction is 100～200 ℃, reaction times is 200～600 minutes, MALEIC ANHYDRIDE in the reactant and FUMARIC ACID TECH GRADE can be partly by hexanodioic acids, phthalic anhydride, a kind of replacement in the m-phthalic acid, MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE account for more than 30% of diacid (acid anhydride) total mole number, dipropylene glycol or neopentyl glycol or polyoxyethylene glycol can be partly by propylene glycol, a kind of replacement in the ethylene glycol, dipropylene glycol or neopentyl glycol or polyoxyethylene glycol account for more than 10% of glycol total mole number, and the molecular-weight average of polyoxyethylene glycol is between 200-800.
4, synthetic method according to claim 2 and the described unsaturated polyester urea resin of claim 3, it is characterized in that, the curing of unsaturated carbamide resin of polyester amide is to use oxidation-reduction trigger systems such as dibenzoyl peroxide-xitix of 1% or methylethyl ketone peroxide-cobalt naphthenate at normal temperatures, the butyl acrylate linking agent that accounts for the vinyl acetate of total mass 20%～50% or account for the methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated carbamide resin of polyester amide crosslinked, or use at normal temperatures and made unsaturated carbamide resin of polyester amide crosslinked in ultraviolet radiation 1-30 minute, or use 1% dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, a kind of and resin alloy in the initiators such as isopropyl benzene hydroperoxide, heating made resin crosslinks in 5-30 minute under 80 ℃-200 ℃, or 180 ℃-230 ℃ following heating made resin crosslinks in 5-30 minute in air atmosphere, and resin solidifies because of molecular weight increases;
Unsaturated carbamide resin of polyester amide solidifies preceding available 5%～30% water dilution reduces system viscosity, favourable forming process, and the resin after the curing can continue heating under 180 ℃-230 ℃ in air atmosphere made state of cure raising, intensity increase in 1-6 hour.
5, according to the synthetic method of the described unsaturated carbamide resin of polyester amide of claim 2; it is characterized in that; after the unsaturated carbamide resin of polyester amide preparation is finished; can add the trimethylolpropane allyl ether that accounts for unsaturated carbamide resin of polyester amide total mass 8%～30%; nitrogen protection in former synthesizer; electronic stirring, 120-170 ℃ was reacted 1-3 hour down, obtains the end capped unsaturated carbamide resin of polyester amide of trimethylolpropane allyl ether.
6, synthetic method according to the end capped unsaturated carbamide resin of polyester amide of the described trimethylolpropane allyl ether of claim 5, it is characterized in that, the curing of the end capped unsaturated carbamide resin of polyester amide of trimethylolpropane allyl ether is to use oxidation-reduction trigger systems such as dibenzoyl peroxide-xitix of 1% or methylethyl ketone peroxide-cobalt naphthenate at normal temperatures, the butyl acrylate linking agent that accounts for the vinyl acetate of total mass 20%～50% or account for the methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated carbamide resin of polyester amide crosslinked, or use at normal temperatures and made the end capped unsaturated carbamide resin of polyester amide of trimethylolpropane allyl ether crosslinked in ultraviolet radiation 1-30 minute, it is good to have the sky dryness after the resin crosslinks, the characteristics that curing speed is fast.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103387668A (en) * | 2012-05-07 | 2013-11-13 | 北京化工大学 | Preparation method of aliphatic polyester amide with urea bond |
| CN105949457A (en) * | 2016-05-13 | 2016-09-21 | 湖南大学 | Flexible unsaturated polyester-urea amide resin and synthesis method thereof |
| CN106074358A (en) * | 2016-06-27 | 2016-11-09 | 林春梅 | A kind of Thermosensitive Material Used for Controlled Releasing of Medicine and preparation method thereof |
| CN107602851A (en) * | 2016-07-11 | 2018-01-19 | 郭文迅 | A kind of water-based self-initiating On Visible Light Cured Resin and its preparation method and application |
| CN109705339A (en) * | 2017-10-26 | 2019-05-03 | 南京曦浪新材料科技有限公司 | A kind of water-soluble multifunctional resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100489009C (en) * | 2005-10-13 | 2009-05-20 | 郭文迅 | Degradable unsaturated carbamide resin of polyester amide, and synthetic method |
-
2007
- 2007-04-26 CN CN2007100348132A patent/CN101293955B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387668A (en) * | 2012-05-07 | 2013-11-13 | 北京化工大学 | Preparation method of aliphatic polyester amide with urea bond |
| CN103387668B (en) * | 2012-05-07 | 2015-10-28 | 北京化工大学 | With the preparation method of the aliphatic polyester amide of urea key |
| 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 |
| CN102702512B (en) * | 2012-06-25 | 2016-08-24 | 湖南工业大学 | Polyester amide urea that degradable is saturated and its preparation method and application |
| CN105949457A (en) * | 2016-05-13 | 2016-09-21 | 湖南大学 | Flexible unsaturated polyester-urea amide resin and synthesis method thereof |
| CN106074358A (en) * | 2016-06-27 | 2016-11-09 | 林春梅 | A kind of Thermosensitive Material Used for Controlled Releasing of Medicine and preparation method thereof |
| CN107602851A (en) * | 2016-07-11 | 2018-01-19 | 郭文迅 | A kind of water-based self-initiating On Visible Light Cured Resin and its preparation method and application |
| CN109705339A (en) * | 2017-10-26 | 2019-05-03 | 南京曦浪新材料科技有限公司 | A kind of water-soluble multifunctional resin and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101293955B (en) | 2012-04-18 |
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