CN103214626A - Method for synthesizing unsaturated polyester resin by utilizing glycerol and phthalic anhydride by-product - Google Patents
Method for synthesizing unsaturated polyester resin by utilizing glycerol and phthalic anhydride by-product Download PDFInfo
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- CN103214626A CN103214626A CN2013101098252A CN201310109825A CN103214626A CN 103214626 A CN103214626 A CN 103214626A CN 2013101098252 A CN2013101098252 A CN 2013101098252A CN 201310109825 A CN201310109825 A CN 201310109825A CN 103214626 A CN103214626 A CN 103214626A
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Abstract
The invention relates to the preparation of a high polymer material and in particular relates to a method for synthesizing unsaturated polyester resin by utilizing glycerol and phthalic anhydride by-product. The method comprises the following steps of: adding 10-20 parts by weight of glycerol, 35-55 parts by weight of phthalic anhydride by-product, 10-15 parts by weight of fumaric acid, 5-7 parts by weight of maleic anhydride, 10-15 parts by weight of propylene glycol and 200ppm-400ppm of esterification catalyst to a reactor with a thermometer, a distillation condensing device and a stirring device; heating up to 155 DEG C to 165 DEG C for discharging water under stirring; heating up to 205 DEG C to 215 DEG C after preserving the heat for 2-3 hours; cooling to 180 DEG C or lower for adding auxiliary materials when an acid value is 50 mgKOH/g-65mgKOH/g through the reaction; and diluting by 25-35 parts by weight of styrene to obtain a finished product. During a reaction method, the method for synthesizing unsaturated polyester resin by utilizing glycerol and phthalic anhydride by-product is easy to control, low in cost, excellent in performances of synthesized novel unsaturated polyester resin and suitable for glass fiber reinforced composite materials.
Description
Technical field
The present invention relates to the manufacturing of macromolecular material, specifically is a kind of method of utilizing glycerine and the synthetic unsaturated polyester resin of by-product of benzoic anhydride.
Background technology
By-product of benzoic anhydride refers to the thing that gently boils that produces with in the o xylene oxidation legal system phthalic anhydride process, and major ingredient is phthalic anhydride (PA), phenylformic acid (BA) and a little unknown impuritie.In producing, it is sold with ultralow valency as waste in the past, also hide some dangers in the time of the waste resource for environmental pollution.Technical grade glycerine is cheap, is widely used in fields such as papermaking, printing, coating, because of its structure is a trihydroxy-, and the following and diprotic acid reaction of high temperature, molecular weight is wayward, and is actually rare in the application in unsaturated polyester field.The conventional dibasic alcohol price height of synthetic unsaturated polyester resin, and to fluctuate indefinite throughout the year, and very big to the product cost influence.
For synthesizing of unsaturated polyester resin material, the record that utilizes glycerine or the synthetic unsaturated polyester resin of by-product of benzoic anhydride is arranged at present.For example Chinese patent 201110113843.9 discloses a kind of method of utilizing the synthetic unsaturated polyester resin of glycerine, main monoprotic acid (phenylformic acid or Glacial acetic acid), the diprotic acid (FUMARIC ACID TECH GRADE, methylene-succinic acid, maleic acid etc.) and glycerine and the synthetic unsaturated polyester resin of part dibasic alcohol of adopting, the phenylformic acid of its use and part dibasic alcohol price height, big to cost impact, and do not have the phthalic anhydride of interpolation in the product and easily cause the toughness of products deficiency.Chinese patent 200810028664.3 discloses a kind of unsaturated polyester resin that utilizes the by-product of benzoic anhydride modification, the main synthetic unsaturated polyester resin of by-product of benzoic anhydride, MALEIC ANHYDRIDE, phthalic anhydride, propylene glycol, ethylene glycol and Diethylene Glycol that adopts, though effectively utilize the phthalic anhydride waste, but the use of a large amount of high price high-quality dibasic alcohol has improved cost, and because of the influence of by-product of benzoic anhydride color depth, high-quality alcohol can't effectively improve finished color.
Summary of the invention
Technical problem to be solved by this invention is, provides that a kind of raw materials cost is low, the method for utilizing glycerine and the synthetic unsaturated polyester resin of by-product of benzoic anhydride of good product performance.
The method of glycerine and the synthetic unsaturated polyester resin of by-product of benzoic anhydride of utilizing of the present invention is: thermometer is being housed, the distillation condensing works, the glycerine that adds 10～20 parts of mass fractions in the reactor of whipping appts, 35～55 parts by-product of benzoic anhydride, 10～15 parts FUMARIC ACID TECH GRADE, 5～7 parts MALEIC ANHYDRIDE, 10～15 parts propylene glycol and 200～400ppm esterifying catalyst, under agitation be heated to 155 ℃～165 ℃ water outlets, hold temperature after 2～3 hours, be warming up to 205 ℃～215 ℃, be cooled to the auxiliary material of adding below 180 ℃ 800ppm when reacting, be diluted to finished product with 25～35 parts of vinylbenzene at last to acid value 50～65mgKOH/g.
Described esterifying catalyst is phosphoric acid or phosphorous acid.
Described auxiliary material is liquid paraffin or semi-refined wax.
The present invention utilizes phthalic anhydride and phenylformic acid and glycerine reaction in the by-product of benzoic anhydride, consume the part of hydroxyl in the glycerol molecule structure, extremely finish with binary acid or anhydride (FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, phthalic anhydride etc.) and dibasic alcohol (propylene glycol, Diethylene Glycol etc.) reaction again.Molecular weight is easy to control during reaction, and is with low cost, and synthesizing new unsaturated polyester resin excellent property is applicable to that glass strengthens the class matrix material.
Embodiment
The embodiment of the invention is as follows:
In the reactor that thermometer, distillation condensing works (chuck is arranged), whipping appts are housed, add (below be mass parts) 20 parts of glycerine, 45 parts of by-product of benzoic anhydride, 10 parts of FUMARIC ACID TECH GRADE, 10 parts of MALEIC ANHYDRIDE, 15 parts of propylene glycol and 200～400ppm esterifying catalyst phosphoric acid, under agitation be heated to 160 ℃ of water outlets, hold temperature after 2 hours, be warming up to 215 ℃, when reacting to acid value 62mgKOH/g, be cooled to the semi-refined wax of adding below 180 ℃ 800ppm and fully stir, be diluted to finished product with 30% vinylbenzene at last.
The product performance test result of the embodiment of the invention is as follows:
1, product chemical property:
Above-mentioned gel time testing method: add 0.3% promotor in the 100 gram resins, the 1ml solidifying agent, 25 degree stir the constant temperature test.
2, measuring mechanical property:
3, processing property testing ﹕
| Test event | This product test result | Market product test result at the same level |
| 1. surface drying | The 30min surface is absolutely dry | The 50min surface is absolutely dry |
| 2. shrinking percentage | 2.1% | 2.2% |
4, test piece test:
| Test event | Testing method |
| 1. tensile strength (Mpa) | GB/T2567-2008 |
| 2. tensile modulus (Mpa) | GB/T2567-2008 |
| 3. flexural strength (Mpa) | GB/T2567-2008 |
| 4. modulus in flexure (Mpa) | GB/T2567-2008 |
| 5. tension set (%) | GB/T2567-2008 |
| Heat-drawn wire (℃) | GB/T1634.2-2004 |
The test piece preparatory condition:
In 1 part of resin, add 0.3% promotor, 1% solidifying agent, room temperature (25 ℃) left standstill 24 hours after solidifying, and spent baking oven constant temperature 16 hours, test performance under 25 degree environment in 70.
5, used plant and instrument:
Rotational viscosimeter (BrookField Co.), moisture determination instrument (MettlerToledo Co.), tension testing machine (High Speed Rail Testing Instruments company limited), thermal distortion instrument (inscription Yu electronics technology company limited), cone-plate viscosity apparatus (BrookField Co.), Water Tank with Temp.-controlled (the permanent instrument plant in sky, Ningbo).
6, conclusion:
The product of the embodiment of the invention makes full use of phenylformic acid and phthalic anhydride in the phthalic anhydride waste, has brought into play glycerine polyfunctional group characteristic simultaneously, the synthetic resin no matter voltinism still be rerum natura all than market product excellence at the same level, and cost advantage is obvious.Can be applied to glasses such as flowerpot and Pei spare ﹑ization Fen Chi ﹑ small-bore pipeline and accessory and strengthen the class field of compound material.
Claims (3)
1. method of utilizing the synthetic unsaturated polyester resin of glycerine and by-product of benzoic anhydride, it is characterized in that: thermometer is being housed, the distillation condensing works, the glycerine that adds 10～20 parts of mass fractions in the reactor of whipping appts, 35～55 parts by-product of benzoic anhydride, 10～15 parts FUMARIC ACID TECH GRADE, 5～7 parts MALEIC ANHYDRIDE, 10～15 parts propylene glycol and 200～400ppm esterifying catalyst, under agitation be heated to 155 ℃～165 ℃ water outlets, hold temperature after 2～3 hours, be warming up to 205 ℃～215 ℃, be cooled to the auxiliary material of adding below 180 ℃ 800ppm when reacting, be diluted to finished product with 25～35 parts of vinylbenzene at last to acid value 50～65 mgKOH/g.
2. the method for utilizing glycerine and the synthetic unsaturated polyester resin of by-product of benzoic anhydride according to claim 1, it is characterized in that: described esterifying catalyst is phosphoric acid or phosphorous acid.
3. the method for utilizing glycerine and the synthetic unsaturated polyester resin of by-product of benzoic anhydride according to claim 1, it is characterized in that: described auxiliary material is liquid paraffin or semi-refined wax.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310109825.2A CN103214626B (en) | 2013-03-29 | 2013-03-29 | Method for synthesizing unsaturated polyester resin by utilizing glycerol and phthalic anhydride by-product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310109825.2A CN103214626B (en) | 2013-03-29 | 2013-03-29 | Method for synthesizing unsaturated polyester resin by utilizing glycerol and phthalic anhydride by-product |
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| Publication Number | Publication Date |
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| CN103214626A true CN103214626A (en) | 2013-07-24 |
| CN103214626B CN103214626B (en) | 2015-04-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307930A (en) * | 2000-04-27 | 2001-11-02 | Toshiba Chem Corp | Coil impregnating resin composition |
| CN101307138A (en) * | 2008-06-05 | 2008-11-19 | 中山联成化学工业有限公司 | Unsaturated polyester resin modified by by-product of benzoic anhydride |
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
-
2013
- 2013-03-29 CN CN201310109825.2A patent/CN103214626B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307930A (en) * | 2000-04-27 | 2001-11-02 | Toshiba Chem Corp | Coil impregnating resin composition |
| CN101307138A (en) * | 2008-06-05 | 2008-11-19 | 中山联成化学工业有限公司 | Unsaturated polyester resin modified by by-product of benzoic anhydride |
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
Non-Patent Citations (2)
| Title |
|---|
| 王树銮等: "用绿色原料甘油制备不饱和聚酯树脂的研究", 《济源职业技术学院学报》 * |
| 石顺存，易平贵: "苯酐渣制备邻苯二甲酸二异丁酯增塑剂", 《精细化工》 * |
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| CN103214626B (en) | 2015-04-22 |
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