CN101602849A - Dimer acid modified unsaturated polyester resin and synthetic method thereof - Google Patents
Dimer acid modified unsaturated polyester resin and synthetic method thereof Download PDFInfo
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- CN101602849A CN101602849A CNA2009100438763A CN200910043876A CN101602849A CN 101602849 A CN101602849 A CN 101602849A CN A2009100438763 A CNA2009100438763 A CN A2009100438763A CN 200910043876 A CN200910043876 A CN 200910043876A CN 101602849 A CN101602849 A CN 101602849A
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Abstract
The present invention adopts the method for melt phase polycondensation, adopt dimeracid as reaction monomers first, several copolymerizations in the monomers such as itself and ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, polyoxyethylene glycol, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, hexanodioic acid, phthalic anhydride, m-phthalic acid are obtained unsaturated polyester resin excellent combination property, lower-cost.This resinoid is expected to release 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, drug coating or capsule, medicine slow (control) matrix resin of material, agricultural mulching etc.
Description
Technical field
The present invention relates to chemosynthesis environment and biodegradable macromolecular material and method.Adopting several in the monomers such as ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, polyoxyethylene glycol, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, hexanodioic acid, phthalic anhydride, m-phthalic acid is basic raw material, obtains unsaturated polyester resin excellent combination property, lower-cost with the common polymerization of dimeracid.This resinoid can be used as the body material of 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 coatings additive(s) 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).Water-borne coatings constantly comes into one's own because of its low VOC content.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.
Do not see patent report as yet with dimer acid modified unsaturated polyester resin, there is no other people and set foot in.The dimeracid raw material is easy to get nontoxic, with low cost, has outstanding water tolerance, snappiness with dimer acid modified unsaturated polyester resin, and more traditional unsaturated polyester resin is greatly improved on performance, so the new patent of application is protected.This resinoid has potential using value at 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 dimer acid modified unsaturated polyester resin and synthetic method thereof are proposed, can synthesize with it and to obtain good comprehensive properties, nontoxic, lower-cost unsaturated polyester resin, 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, the constitutional features of described dimer acid modified unsaturated polyester resin is to contain dimeracid residue :-OCO-C in its molecule
34H
62-CO-.
Two of technical solution of the present invention is; the step of the synthetic method of described dimer acid modified unsaturated polyester resin is: MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE, propylene glycol or ethylene glycol or Diethylene Glycol or neopentyl glycol or polyoxyethylene glycol are mixed by certain mol proportion with dimeracid; 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 of semi-solid state.
Described MALEIC ANHYDRIDE of this synthetic method or FUMARIC ACID TECH GRADE: propylene glycol or ethylene glycol or Diethylene Glycol or neopentyl glycol or polyoxyethylene glycol: the mol ratio of dimeracid 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, propylene glycol or ethylene glycol or Diethylene 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 polyester resin preparation is finished; can add the trimethylolpropane allyl ether that accounts for unsaturated polyester resin total mass 8%～30%; nitrogen protection in former synthesizer; electronic stirring; 120-170 ℃ was reacted 1-3 hour down, obtains the end capped unsaturated polyester resin of trimethylolpropane allyl ether.
The curing of unsaturated polyester resin 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 methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated polyester resin crosslinked, or use 0%～5% benzoin dimethylether or 1173 light triggers to make unsaturated polyester resin crosslinked at normal temperatures with 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 polyester resin solidifies preceding available 15%～300% 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 resin should minimize cost, the consideration of novel, nontoxic, excellent combination property, inexpensive raw materials such as employing dimeracid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, phthalic anhydride, m-phthalic acid, hexanodioic acid, propylene glycol, ethylene glycol, Diethylene Glycol, neopentyl glycol, polyoxyethylene glycol have been designed, select relatively mild reaction conditions, synthetic prepared excellent combination property, nontoxic, lower-cost unsaturated polyester resin.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 polyester resin:
The synthetic unsaturated polyester resin all characterizes with FT-IR.Accompanying drawing 1 is the IR spectrogram (mol ratio: dimeracid/MALEIC ANHYDRIDE/Tetra hydro Phthalic anhydride/ethylene glycol/Diethylene Glycol=0.2/2.0/2.0/2.2/2.1) of unsaturated polyester resin.Its charateristic avsorption band is: 2925～2930, the absorption peak at 2850～2860cm-1 place is the υ c-H of fatty chain alkyl, at 1722cm-1 strong C=O stretching vibration charateristic avsorption band is arranged, C=C stretching vibration charateristic avsorption band is arranged at the 1383cm-1 place, at 1157cm-1 C-O stretching vibration absorption peak is arranged, at 2919cm
-1C-H stretching vibration absorption peak is arranged, at 3300-3600cm
-1Wide-COOH the absorption peak at place shows that residual-COOH is arranged in the polymkeric substance.Experimental result shows the structure and theoretical expect consistent of all synthetic polymers.
Unsaturated polyester resin performance of the present invention:
1) curing performance
The curing of unsaturated polyester resin 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 methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated polyester resin crosslinked; Or use 0%～5% benzoin dimethylether or 1173 light triggers to make unsaturated polyester resin crosslinked at normal temperatures with 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 polyester resin solidifies preceding available 15%～300% 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) mechanical property
The synthetic unsaturated polyester resin is rich in dimeracid residue :-OCO-C
34H
62-CO-gives material good snappiness.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-12000W during photocuring, and irradiation time was advisable with 15 seconds-10 minutes.As lamp is apart from 20cm, 12 minutes crosslinking curings of 1000W ultra violet lamp in air atmosphere behind the mixed water 20% of embodiment 1 synthetic unsaturated polyester resin, adding 4% light trigger 1173, the sticking power that records is one-level, and pencil hardness is 5H.
Description of drawings
Fig. 1 is the IR spectrogram (mol ratio: dimeracid/MALEIC ANHYDRIDE/Tetra hydro Phthalic anhydride/ethylene glycol/Diethylene Glycol=0.2/2.0/2.0/2.2/2.1) of unsaturated polyester resin
Embodiment
Embodiment 1: one of synthetic method of unsaturated polyester resin:
With 2.0 moles of MALEIC ANHYDRIDE, 2.0 moles of phthalic anhydrides, 0.2 mole of dimeracid and 2.2 moles of ethylene glycol, 2.1 moles of Diethylene Glycols mixing, pack in the 250ml there-necked flask of being with water trap, place silicone oil bath, electronic stirring is warming up to 150 ℃, and 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 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 faint yellow transparent thick liquid nano unsaturated polyester resin after the cooling.
Claims (6)
1, the novel unsaturated polyester resin of a class is characterized in that, has adopted dimeracid to do one of reaction monomers in its building-up process;
Adopting several in the monomers such as ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, polyoxyethylene glycol, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, hexanodioic acid, phthalic anhydride, m-phthalic acid is basic raw material, obtains unsaturated polyester resin excellent combination property, lower-cost with the common polymerization of dimeracid;
The general structure of unsaturated polyester is:
R is C=C in the formula, can be partly by phenyl ring, and (CH
2)
4Replace Deng group, R ' is (CH
2)
2, CH (CH
3) CH
2, CH
2C (CH
3)
2CH
2, CH
2CH
2OCH
2CH
2, (CH
2CH
2O)
pA kind of Deng in the group, the p value is between 4～20, and m, n are the mole number of the chain link of diacid (acid anhydride) binary alcohol esters.
2, the synthetic method of the unsaturated polyester resin of claim 1 is characterized in that, this method is:
MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE, phthalic anhydride or hexanodioic acid or m-phthalic acid, ethylene glycol or Diethylene Glycol or propylene glycol or neopentyl glycol or polyoxyethylene glycol are mixed by certain mol proportion with dimeracid; 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 resin of semi-solid state.
3, synthetic method according to the described unsaturated polyester resin of claim 2, it is characterized in that, described MALEIC ANHYDRIDE of synthetic method or FUMARIC ACID TECH GRADE: ethylene glycol or Diethylene Glycol or propylene glycol or neopentyl glycol or polyoxyethylene glycol: the mol ratio of dimeracid 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.
4, synthetic method according to the described unsaturated polyester resin of claim 2, it is characterized in that, the curing of unsaturated polyester resin 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 methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated polyester resin crosslinked, or use 0%～5% benzoin dimethylether or 1173 light triggers to make unsaturated polyester resin crosslinked at normal temperatures with 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 polyester resin solidifies preceding available 15%～300% 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 polyester resin of claim 2; it is characterized in that; after the unsaturated polyester resin preparation is finished; can add the trimethylolpropane allyl ether that accounts for unsaturated polyester resin total mass 8%～30%; nitrogen protection in former synthesizer; electronic stirring, 120-170 ℃ was reacted 1-3 hour down, obtains the end capped unsaturated polyester resin of trimethylolpropane allyl ether.
6, synthetic method according to the end capped unsaturated polyester resin of the described trimethylolpropane allyl ether of claim 5, it is characterized in that, the curing of the end capped unsaturated polyester resin 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 methyl methacrylate of total mass 20%～50% or account for total mass 20%～50% makes unsaturated polyester resin crosslinked, or use 0%～5% benzoin dimethylether or 1173 light triggers to make the end capped unsaturated polyester resin of trimethylolpropane allyl ether crosslinked at normal temperatures with 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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Application publication date: 20091216 |