CN103275309A - Phosphorous flame-retardant unsaturated polyester resin and preparation method thereof - Google Patents
Phosphorous flame-retardant unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN103275309A CN103275309A CN2013102590761A CN201310259076A CN103275309A CN 103275309 A CN103275309 A CN 103275309A CN 2013102590761 A CN2013102590761 A CN 2013102590761A CN 201310259076 A CN201310259076 A CN 201310259076A CN 103275309 A CN103275309 A CN 103275309A
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Abstract
The invention discloses phosphorous flame-retardant unsaturated polyester resin and a preparation method thereof. A formula of the phosphorous flame-retardant unsaturated polyester resin comprises the following components in percentage by weight: 18.39%-25.04% of maleic anhydride, 8.47%-25.35% of DOPOMA (2-[10-(9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide-10-yl)] maleic acid), 13.45%-18.91% of phthalic anhydride, 6.80%-7.70% of glycol, 24.26%-27.70% of propylene glycol, 11.75%-12.95% of diethylene glycol, 5.1%-7% of a water-carrying agent, 0.02% of a catalyst, 0.02% of a polymerization inhibitor, 25%-35% of a cross-linking agent, and 25%-35% of a diluent. The preparation method of the polyester resin comprises the steps of synthesizing the raw material DOPOMA with DOPO and MA at a molar ratio of 1:1.05, adding maleic anhydride, phthalic anhydride, glycol, propylene glycol and diethylene glycol, and directly synthesizing the flame-retardant unsaturated polyester resin with a one-step method.
Description
Technical field
The present invention relates to the technology of preparing of unsaturated polyester resin.
Background technology
Unsaturated polyester resin is to use the most general resin in the reinforced plastics.In the field of reinforced plastics, the thermosetting resin consumption accounts for 75%.The kind of thermosetting resin has a variety of, and wherein the consumption of unsaturated polyester resin is considerably beyond other various resins, because unsaturated polyester resin has particularly advantageous fabrication process condition, and low price.Though for example the resol price is lower than polyester, when solidifying, processing to discharge moisture, form steam, the condition that must adopt higher forming pressure (being generally 8-30MPa) and heat up, thereby need bigger press to produce.Unsaturated polyester resin is not discharged moisture and other by products when processing is solidified, so can be at lower pressure and temperature compacted under.In fact, unsaturated polyester resin is used in a large number and is processed into various goods under normal temperature and the contact pressure, and this is that other resins are incomparable.
Unsaturated polyester resin generally is the polyester macromolecule that has unsaturated link(age) on the molecular chain, be to be formed through polycondensation progressively by unsaturated dibasic acid (acid anhydride), monounsaturated dicarboxylic acid (acid anhydride) and dibasic alcohol, and after finishing, polycondensation adds a certain amount of vinyl monomer such as vinylbenzene, methyl methacrylate etc. while hot, form the liquid resin of thickness, when using, add initiator, promotor etc., copolyreaction can take place, and forms the cancellated polymer of 3 D stereo.
The disclosed phosphorus heterocycle flame-proof copolyester ionomer that contains of patent CN102924702A is on the basis of the polyester structural units that I, II are represented, introduced the structural unit of being represented by III or IV and formed through random copolymerization, this intrinsic viscosity [η] that contains the phosphorus heterocycle copolyester ionomer is 0.2～1.1dL/g.The melt viscosity of the polyester of this technology is not high, and performance fire-retardant, anti-molten drop is not ideal.
Summary of the invention
The purpose of this invention is to provide a kind ofPhosphor-containing flame-proof unsaturated polyester resin and preparation method thereof.
The present invention isPhosphor-containing flame-proof unsaturated polyester resin and preparation method thereof, the phosphor-containing flame-proof unsaturated polyester resin, by weight percentage, its component is: MALEIC ANHYDRIDE 18.39% ~ 25.04%, DOPOMA8.47% ~ 25.35%, Tetra hydro Phthalic anhydride 13.45% ~ 18.91%, ethylene glycol 6.80% ~ 7.70%, propylene glycol 24.26% ~ 27.70%, glycol ether 11.75% ~ 12.95%, band aqua 5.1% ~ 7%, catalyzer 0.02%, stopper 0.02%, linking agent, thinner 25% ~ 35%.
The preparation method of phosphor-containing flame-proof unsaturated polyester resin prepares burden by the above component and proportioning thereof, the steps include:
(1) described DOPOMA be by 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide compound and maleic anhydride obtain with the molar ratio reaction of 1:1.05, its preparation process is:
In the there-necked flask that agitator, thermometer, reflux condensing tube are housed, the tetrahydrofuran (THF) of quality such as adding and toluene mixing solutions, DOPO and MALEIC ANHYDRIDE drop into stirring heating with the mol ratio of 1:1.05; Stopped reaction and be cooled to room temperature behind the insulation reaction 24h adds an amount of dimethylbenzene in the solution and constantly stirs, system layering, and lower floor is blackish green thick liquid, the upper strata is faint yellow clarified liq; Separate to obtain lower floor's thick liquid, repeatedly wash with dimethylbenzene white powder powder material is wherein removed, place dry 48h in 120 ℃ the baking oven at last, take out and be cooled to room temperature, with solid abrasive, obtain pale yellow powder crystalline solid;
(2) preparation process of phosphor-containing flame-proof unsaturated polyester resin is:
In the there-necked flask of 100ml, add MALEIC ANHYDRIDE, DOPOMA, Tetra hydro Phthalic anhydride, ethylene glycol, propylene glycol, glycol ether, dimethylbenzene is opened stirring, slowly heat up, system became little glistening yellow clear transparent liquid when temperature was 80 ℃, when temperature reaches 120 ℃, was warming up to 140 ℃ with 20 minutes, continue slowly to be warming up to 180 ℃, the temperature of reaction is no more than 200 ℃, and insulation reaction to acid value is lower than 30mgKOH/g, when acid value arrives when suitable the dimethylbenzene suction filtration is fallen, add stopper when being cooled to 140 ℃, constantly stir cooling, add prior load weighted vinylbenzene and stir 0.5h fast and make the system stable homogeneous when temperature reaches 80 ℃, last discharging can obtain the phosphor-containing flame-proof unsaturated polyester resin.
Usefulness of the present invention isAt first adopt 9 by molecular designing, 10 1 dihydros, one 9 one oxa-one 10 one phospho hetero phenanthrenes, one 10 monoxide (DOPO) and maleic anhydride (MA) obtain DOPOMA with the molar ratio reaction of 1:1.05, and synthesize flame-retarded unsaturated polyester resin as raw material, it has introduced the element phosphor with flame retardant properties in macromolecular chain, synthesized the unsaturated polyester resin with flame retardant properties.
Embodiment
The present invention is finished by following technical scheme, DOPO and MA be with the mole synthesis material DOPOMA recently of 1:1.05, and add MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, ethylene glycol, propylene glycol, glycol ether and adopt single stage method directly to synthesize flame-retarded unsaturated polyester resin.
Based on the total mass of preparation phosphor-containing flame-proof unsaturated polyester resin, by weight percentage, phosphor-containing flame-proof unsaturated polyester resin prescription is:
MALEIC ANHYDRIDE 18.39% ~ 25.04%, DOPOMA8.47% ~ 25.35%, Tetra hydro Phthalic anhydride 13.45% ~ 18.91%, ethylene glycol 6.80% ~ 7.70%, propylene glycol 24.26% ~ 27.70%, glycol ether 11.75% ~ 12.95%, band aqua 5.1% ~ 7%, catalyzer 0.02%, stopper 0.02%, linking agent, thinner 25% ~ 35%.
The preparation process of phosphor-containing flame-proof unsaturated polyester resin is:
In the there-necked flask of 100ml, add MALEIC ANHYDRIDE, DOPOMA, Tetra hydro Phthalic anhydride, ethylene glycol, propylene glycol, glycol ether, dimethylbenzene.Open stirring, slowly heat up.System became little glistening yellow clear transparent liquid when temperature was 80 ℃.When temperature reaches 120 ℃, be warming up to 140 ℃ with 20 minutes, continue slowly to be warming up to 180 ℃ (1.5h consuming time).The temperature of reaction does not surpass 200 ℃ at last, and insulation reaction to acid value is lower than 30mgKOH/g.When acid value arrives when suitable the dimethylbenzene suction filtration is fallen, add stopper when being cooled to 140 ℃, constantly stir cooling.Add prior load weighted vinylbenzene and stir 0.5h fast and make the system stable homogeneous when temperature reaches 80 ℃, last discharging can obtain the phosphor-containing flame-proof unsaturated polyester resin.
Below be embodiments of the invention, but the present invention is not limited in the following example.
Embodiment 1.
In the there-necked flask of 100ml, add 13.72 parts of MALEIC ANHYDRIDE, DOPOMA4.71 part, 10.36 parts of Tetra hydro Phthalic anhydrides, 4.20 parts of ethylene glycol, 15.40 parts of propylene glycol, 7.20 parts of glycol ethers, 2.80 parts of dimethylbenzene, 0.0100 part of catalyzer.Open stirring, slowly heat up.System became little glistening yellow clear transparent liquid when temperature was 80 ℃.When temperature reaches 120 ℃, be warming up to 140 ℃ with 20 minutes, continue slowly to be warming up to 180 ℃ (1.5h consuming time).The temperature of reaction does not surpass 200 ℃ at last, and insulation reaction to acid value is lower than 30mgKOH/g.When acid value arrives 10.09mgKOH/g, the dimethylbenzene suction filtration is fallen, add 0.0100 part of stopper when being cooled to 140 ℃, constantly stir cooling.Add 13.9 parts of prior load weighted vinylbenzene when temperature reaches 80 ℃, stir 0.5h fast and make the system stable homogeneous, last discharging can obtain the phosphor-containing flame-proof unsaturated polyester resin.
Embodiment 2.
In the there-necked flask of 100ml, add 12.74 parts of MALEIC ANHYDRIDE, DOPOMA9.42 part, 9.62 parts of Tetra hydro Phthalic anhydrides, 4.2 parts of ethylene glycol, 15.4 parts of propylene glycol, 7.2 parts of glycol ethers, 2.93 parts of dimethylbenzene.Open stirring, slowly heat up.System became little glistening yellow clear transparent liquid when temperature was 80 ℃.When temperature reaches 120 ℃, be warming up to 140 ℃ with 20 minutes, continue slowly to be warming up to 180 ℃ (1.5h consuming time).The temperature of reaction does not surpass 200 ℃ at last, and insulation reaction to acid value is lower than 30mgKOH/g.When acid value arrives 22.4mgKOH/g, the dimethylbenzene suction filtration is fallen, add 0.1172 part of stopper when being cooled to 140 ℃, constantly stir cooling.Add load weighted 14.64 parts of vinylbenzene in advance when temperature reaches 80 ℃, stir 0.5h fast and make the system stable homogeneous, last discharging can obtain the phosphor-containing flame-proof unsaturated polyester resin.
Claims (7)
1. phosphor-containing flame-proof unsaturated polyester resin, by weight percentage, its component is: MALEIC ANHYDRIDE 18.39% ~ 25.04%, DOPOMA8.47% ~ 25.35%, Tetra hydro Phthalic anhydride 13.45% ~ 18.91%, ethylene glycol 6.80% ~ 7.70%, propylene glycol 24.26% ~ 27.70%, glycol ether 11.75% ~ 12.95%, band aqua 5.1% ~ 7%, catalyzer 0.02%, stopper 0.02%, linking agent, thinner 25% ~ 35%.
2. phosphor-containing flame-proof unsaturated polyester resin according to claim 1 is characterized in that propylene glycol is 1,2 propylene glycol.
3. phosphor-containing flame-proof unsaturated polyester resin according to claim 1, it is characterized in that being with aqua is dimethylbenzene.
4. phosphor-containing flame-proof unsaturated polyester resin according to claim 1 is characterized in that stopper is Resorcinol.
5. phosphor-containing flame-proof unsaturated polyester resin according to claim 1 is characterized in that catalyzer is tosic acid.
6. phosphor-containing flame-proof unsaturated polyester resin according to claim 1 is characterized in that linking agent, thinner are vinylbenzene.
7. the preparation method of phosphor-containing flame-proof unsaturated polyester resin prepares burden by the described component of claim 1 and proportioning thereof, the steps include:
(1) described DOPOMA be by 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide compound and maleic anhydride obtain with the molar ratio reaction of 1:1.05, its preparation process is:
In the there-necked flask that agitator, thermometer, reflux condensing tube are housed, the tetrahydrofuran (THF) of quality such as adding and toluene mixing solutions, DOPO and MALEIC ANHYDRIDE drop into stirring heating with the mol ratio of 1:1.05; Stopped reaction and be cooled to room temperature behind the insulation reaction 24h adds an amount of dimethylbenzene in the solution and constantly stirs, system layering, and lower floor is blackish green thick liquid, the upper strata is faint yellow clarified liq; Separate to obtain lower floor's thick liquid, repeatedly wash with dimethylbenzene white powder powder material is wherein removed, place dry 48h in 120 ℃ the baking oven at last, take out and be cooled to room temperature, with solid abrasive, obtain pale yellow powder crystalline solid;
(2) preparation process of phosphor-containing flame-proof unsaturated polyester resin is:
In the there-necked flask of 100ml, add MALEIC ANHYDRIDE, DOPOMA, Tetra hydro Phthalic anhydride, ethylene glycol, propylene glycol, glycol ether, dimethylbenzene is opened stirring, slowly heat up, system became little glistening yellow clear transparent liquid when temperature was 80 ℃, when temperature reaches 120 ℃, was warming up to 140 ℃ with 20 minutes, continue slowly to be warming up to 180 ℃, the temperature of reaction is no more than 200 ℃, and insulation reaction to acid value is lower than 30mgKOH/g, when acid value arrives when suitable the dimethylbenzene suction filtration is fallen, add stopper when being cooled to 140 ℃, constantly stir cooling, add prior load weighted vinylbenzene and stir 0.5h fast and make the system stable homogeneous when temperature reaches 80 ℃, last discharging can obtain the phosphor-containing flame-proof unsaturated polyester resin.
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Cited By (7)
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| CN104650299A (en) * | 2015-01-31 | 2015-05-27 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for buttons and preparation method of unsaturated polyester resin |
| CN104926998A (en) * | 2015-01-31 | 2015-09-23 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin used for bulk molding compound and preparation method thereof |
| CN106046338A (en) * | 2016-07-18 | 2016-10-26 | 同济大学 | Thermoset polylactic acid with intrinsically flame retardant performance and preparation method thereof |
| CN106432676A (en) * | 2016-09-28 | 2017-02-22 | 齐鲁工业大学 | Preparation method of N/P/nano synergistic flame-retardant waterborne polyurethane dispersion liquid |
| CN106633021A (en) * | 2014-04-09 | 2017-05-10 | 长兴材料工业股份有限公司 | Modified phosphorus-containing unsaturated polyesters |
| CN108359085A (en) * | 2018-01-02 | 2018-08-03 | 河北晨阳工贸集团有限公司 | Applied to the dewatering process in alkyd or polyester resin synthesis |
| CN109181255A (en) * | 2018-08-24 | 2019-01-11 | 安徽汇创新材料有限公司 | A kind of flame-retarded unsaturated polyester resin glass reinforced plastic |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633021A (en) * | 2014-04-09 | 2017-05-10 | 长兴材料工业股份有限公司 | Modified phosphorus-containing unsaturated polyesters |
| CN104650299A (en) * | 2015-01-31 | 2015-05-27 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for buttons and preparation method of unsaturated polyester resin |
| CN104926998A (en) * | 2015-01-31 | 2015-09-23 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin used for bulk molding compound and preparation method thereof |
| CN106046338A (en) * | 2016-07-18 | 2016-10-26 | 同济大学 | Thermoset polylactic acid with intrinsically flame retardant performance and preparation method thereof |
| CN106432676A (en) * | 2016-09-28 | 2017-02-22 | 齐鲁工业大学 | Preparation method of N/P/nano synergistic flame-retardant waterborne polyurethane dispersion liquid |
| CN106432676B (en) * | 2016-09-28 | 2018-12-25 | 齐鲁工业大学 | A kind of preparation method of N/P/ nanometers of synergistic extinguishing waterborn polyurethane dispersion liquid |
| CN108359085A (en) * | 2018-01-02 | 2018-08-03 | 河北晨阳工贸集团有限公司 | Applied to the dewatering process in alkyd or polyester resin synthesis |
| CN108359085B (en) * | 2018-01-02 | 2020-07-28 | 河北晨阳工贸集团有限公司 | Dehydration process applied to synthesis of alkyd or polyester resin |
| CN109181255A (en) * | 2018-08-24 | 2019-01-11 | 安徽汇创新材料有限公司 | A kind of flame-retarded unsaturated polyester resin glass reinforced plastic |
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Application publication date: 20130904 |