CN101353555B - Flame-retardant rosin epoxide resin and preparation thereof - Google Patents
Flame-retardant rosin epoxide resin and preparation thereof Download PDFInfo
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- CN101353555B CN101353555B CN2008100295657A CN200810029565A CN101353555B CN 101353555 B CN101353555 B CN 101353555B CN 2008100295657 A CN2008100295657 A CN 2008100295657A CN 200810029565 A CN200810029565 A CN 200810029565A CN 101353555 B CN101353555 B CN 101353555B
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Abstract
The invention provides a flame-retardant epoxy rosin which has a structural formula as the picture and provides a preparation method of the product that includes the steps of carrying out catalytic reaction to the mixed bromized maleic rosin and epichlorohydrin until the reaction is finished, cooling and adding solvent so as to continue the reaction with sodium hydroxide, and then obtaining the product through filtration, washing, drying and decompression after the reaction. The product comes from natural renewable resources, has molecules with a rigid fused ring structure, and has excellent flame retardancy. The method provided by invention is simple and easy to use, and is suitable for large-scale production and application.
Description
Technical field
The present invention relates to a kind of flame-retardant rosin epoxide resin and preparation method thereof.
Background technology
China's rosin abundant information is a kind of natural reproducible data, and is cheap.But there are shortcomings such as easy crystallization, oxidation resistent susceptibility difference and acid number height in rosin itself, it is directly used be restricted.So,, must carry out modification to it for characteristics and the advantage of giving full play to rosin itself.Use its modified product---the bromination maleated rosin is a raw material synthesizing glycidol ester type epoxy resin, not only can enrich the Resins, epoxy kind, improves some performance of Resins, epoxy, can also widen the rosiny range of application, improves its added value.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention provides a kind of rosin and epoxy resin that natural reproducible resource, molecule have the condensed ring rigid structure, have good flame retardant resistance that derives from.
Another object of the present invention is to provide the preparation method of above-mentioned flame-retardant rosin epoxide resin.
Purpose of the present invention is achieved through the following technical solutions: flame-retardant rosin epoxide resin of the present invention has following structural formula:
Flame-retardant rosin epoxide resin of the present invention at room temperature is transparent thick liquid of red-brown or solid, and 1726cm is arranged in infrared spectrogram
-1, 1243cm
-1, 1144cm
-1, 1103cm
-1, 910cm
-1, 850cm
-1, 800cm
-1And 760cm
-1Charateristic avsorption band; Oxirane value is 0.22～0.30 epoxy equivalent (weight)/100 gram resins; Softening temperature is 20～50 ℃.
The preparation method of a kind of flame-retardant rosin epoxide resin provided by the invention specifically comprises the following steps:
(1) bromination maleated rosin and propylene oxide are mixed the back stirring, catalyzed reaction is carried out in heating;
(2) above-mentioned reaction finishes postcooling, adds solvent and sodium hydroxide and reacts;
(3) step (2) gained reaction product after filtration, be washed to halogen ion, drying and after reduced pressure treatment, obtain product.
By weight, the proportioning of each reactive component is in the above-mentioned steps: the proportioning of each reactive component is: 100 parts of bromination maleated rosins, 180～250 parts of epoxy chloropropane, 14～25 parts in 80～100 parts of solvents and sodium hydroxide.More preferably, the proportioning of each reactive component is: 100 parts of bromination maleated rosins, 190～240 parts of epoxy chloropropane, 15～22 parts in 85～95 parts of solvents and sodium hydroxide.
The described catalyzed reaction of step (1) adds the alkaline solution of catalyzer, solid alkali or mass concentration 20～60%, described catalyzer uses tetramethyl ammonium chloride, cetyl trimethylammonium bromide or octadecyl trimethylammonium bromide, and add-on is 0.05～0.6% of a bromination maleated rosin quality; Described alkali is sodium hydroxide or potassium hydroxide, and the add-on of solid alkali is 20～30% of a bromination maleated rosin quality, and the add-on of alkaline solution is 50～100% of a bromination maleated rosin quality.
The temperature of catalyzed reaction is 70～90 ℃ described in the step (1), preferred 75～88 ℃; The time of catalyzed reaction is 3～6 hours, preferred 3.5～5 hours.
Solvent is benzene, toluene or epoxy chloropropane described in the step (2); The temperature of described reaction is 60～70 ℃, and the time is 2～5 hours.
More preferably, the temperature of the described reaction of step (2) is 65～68 ℃, and the time is 2.5～4 hours.
The present invention compared with prior art has following advantage:
1, further expanded the rosiny use range;
2, opened up that epoxide resin material is newly originated, new variety;
3, also have the condensed ring structure in the flame-retardant rosin epoxide resin molecule, its cured product has strong anti-ultraviolet property, is that Examples of alicyclic polymers is distinctive.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) bromination maleated rosin 100 grams and epoxy chloropropane 240 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 85 ℃, add sodium hydroxide 20 grams, the reaction times is 5 hours.
(2) reaction finishes postcooling, adds 80 gram toluene, adds sodium hydroxide 14 grams, and temperature is controlled at 70 ℃, reacts 2 hours.
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the toluene that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
Embodiment 2
The 20 gram sodium hydroxide that add in embodiment 1 step (2) replace with the sodium hydroxide solution of 50 gram mass concentration 40%, and other and embodiment 1 are together.
Embodiment 3
The 20 gram sodium hydroxide that add in embodiment 1 step (2) replace with the sodium hydroxide solution of 100 gram mass concentration 20%, and other and embodiment 1 are together.
Embodiment 4
(1) bromination maleated rosin 100 grams and epoxy chloropropane 235 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 88 ℃, add tetramethyl ammonium chloride 0.4 gram, the reaction times is 4.5 hours.
(2) reaction finishes postcooling, adds 75 gram benzene, adds potassium hydroxide 30 grams, and temperature is controlled at 68 ℃, reacts 2.5 hours.
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the benzene that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
Embodiment 5
The 30 gram potassium hydroxide that add in embodiment 4 steps (2) replace with the potassium hydroxide solution of 80 gram mass concentration 60%, and other and embodiment 1 are together.
Embodiment 6
The 30 gram potassium hydroxide that add in embodiment 4 steps (2) replace with the potassium hydroxide solution of 60 gram mass concentration 40%, and other and embodiment 1 are together.
Embodiment 7
(1) bromination maleated rosin 100 grams and epoxy chloropropane 180 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 90 ℃, adding the 0.05 gram reaction times of tetramethyl ammonium chloride is 5 hours.
(2) reaction finishes postcooling, adds 100 gram toluene, adds sodium hydroxide 20 grams, and temperature is controlled at 60 ℃, reacts 3 hours.
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the toluene that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
Embodiment 8
(1) bromination maleated rosin 100 grams and epoxy chloropropane 190 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 80 ℃, add tetramethyl ammonium chloride 0.05 gram, the reaction times is 6 hours.
(2) reaction finishes postcooling, adds 70 gram epoxy chloropropane, adds sodium hydroxide 22 grams, and temperature is controlled at 65 ℃, reacts 3.5 hours.
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the epoxy chloropropane that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
Embodiment 9
(1) bromination maleated rosin 100 grams and epoxy chloropropane 220 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 90 ℃, add the solution of potassium hydroxide solid 0.35 gram or 20% mass concentration, the reaction times is 3.5 hours.
(2) reaction finishes postcooling, adds 85 gram toluene, adds sodium hydroxide 25 grams, and temperature is controlled at 63 ℃, reacts 3.5 hours.
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the toluene that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
Embodiment 10
(1) bromination maleated rosin 100 grams and epoxy chloropropane 215 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 85 ℃, add cetyl trimethylammonium bromide 0.6 gram, the reaction times is 3 hours,
(2) reaction finishes postcooling, adds 95 gram toluene, adds sodium hydroxide 25 grams, and temperature is controlled at below 70 ℃, reacts 3 hours.
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the toluene that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
Embodiment 11
(1) bromination maleated rosin 100 grams and epoxy chloropropane 250 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 70 ℃, add tetramethyl ammonium chloride 0.20 gram, the reaction times is 5 hours.
(2) reaction finishes postcooling, adds 70 gram benzene, adds sodium hydroxide 23 grams, and temperature is controlled at 67 ℃, reacted 5 hours,
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the benzene that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
Embodiment 12
(1) bromination maleated rosin 100 grams and epoxy chloropropane 200 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, stir and be warmed up to 75 ℃, add octadecyl trimethylammonium bromide 0.55 gram, the reaction times is 4 hours,
(2) reaction finishes postcooling, adds 70 gram toluene, adds sodium hydroxide 20 grams, and temperature is controlled at 65 ℃, reacted 4 hours,
(3) products therefrom filters, and filtrate water is washed till the halogen ion, drying, and the toluene that desolvates that reduces pressure gets the product flame-retardant rosin epoxide resin.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. flame-retardant rosin epoxide resin is characterized in that: have following structural formula:
2. flame-retardant rosin epoxide resin according to claim 1 is characterized in that: being under the room temperature transparent thick liquid of red-brown or solid has 1726cm in infrared spectrogram
-1, 1243cm
-1, 1144cm
-1, 1103cm
-1, 910cm
-1, 850cm
-1, 800cm
-1And 760cm
-1Charateristic avsorption band; Oxirane value is 0.22～0.30 epoxy equivalent (weight)/100 gram resins; Softening temperature is 20～50 ℃.
3. the preparation method of the described flame-retardant rosin epoxide resin of claim 1 is characterized in that: comprise the following steps:
(1) by weight, be with the proportioning of reactive component: 100 parts of bromination maleated rosins, to stir after 180～250 parts of mixing of epoxy chloropropane, catalyzed reaction is carried out in heating, and the temperature of reaction is 70～90 ℃, and the catalyzed reaction time is 3～6 hours;
(2) above-mentioned reaction finishes postcooling, adds by weight, and with the proportioning of reactive component be: 80～100 parts of solvents and sodium hydroxide react for 14～25 parts, and the temperature of reaction is 60～70 ℃, and the time is 2～5 hours;
(3) step (2) gained reaction product after filtration, be washed to halogen ion, drying and after reduced pressure treatment, obtain product.
Flame-retardant rosin epoxide resin according to claim 3 the preparation method, it is characterized in that: by weight, the proportioning of each reactive component is: 100 parts of bromination maleated rosins, 190～240 parts of epoxy chloropropane, 15～22 parts in 85～95 parts of solvents and sodium hydroxide.
Flame-retardant rosin epoxide resin according to claim 3 the preparation method, it is characterized in that: described catalyzed reaction adds the alkaline solution of catalyzer, solid alkali or mass concentration 20～60%.
6. the preparation method of flame-retardant rosin epoxide resin according to claim 5, it is characterized in that: described catalyzer uses tetramethyl ammonium chloride, cetyl trimethylammonium bromide or octadecyl trimethylammonium bromide, and add-on is 0.05～0.6% of a bromination maleated rosin quality; Described alkali is sodium hydroxide or potassium hydroxide, and the add-on of solid alkali is 20～30% of a bromination maleated rosin quality, and the add-on of alkaline solution is 50～100% of a bromination maleated rosin quality.
7. the preparation method of flame-retardant rosin epoxide resin according to claim 5, it is characterized in that: the temperature of described catalyzed reaction is 75～88 ℃; The time of described catalyzed reaction is 3.5～5 hours.
8. the preparation method of flame-retardant rosin epoxide resin according to claim 3, it is characterized in that: the described solvent of step (2) is benzene, toluene or epoxy chloropropane.
9. the preparation method of flame-retardant rosin epoxide resin according to claim 8, it is characterized in that: the temperature of described reaction is 65～68 ℃, the time is 2.5～4 hours.
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| CN2008100295657A CN101353555B (en) | 2008-07-18 | 2008-07-18 | Flame-retardant rosin epoxide resin and preparation thereof |
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| CN2008100295657A CN101353555B (en) | 2008-07-18 | 2008-07-18 | Flame-retardant rosin epoxide resin and preparation thereof |
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| CN101353555A CN101353555A (en) | 2009-01-28 |
| CN101353555B true CN101353555B (en) | 2011-04-27 |
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| CN106554493A (en) * | 2015-09-29 | 2017-04-05 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of Oleum Ricini acidic group flame retardant polyether polyol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297011A (en) * | 2000-11-07 | 2001-05-30 | 东莞理工学院 | Glycide malcopimarate and its preparing process |
| CN1371930A (en) * | 2001-02-27 | 2002-10-02 | 中国林业科学研究院林产化学工业研究所 | Process for preparing outdoor weathe resistance epoxy resin |
| CN1793224A (en) * | 2005-12-20 | 2006-06-28 | 东莞理工学院 | Composite of non-halogen flame retarded type epoxy resin and semi-solidified sheet containing same composite and copper foil clad laminated board |
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2008
- 2008-07-18 CN CN2008100295657A patent/CN101353555B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297011A (en) * | 2000-11-07 | 2001-05-30 | 东莞理工学院 | Glycide malcopimarate and its preparing process |
| CN1371930A (en) * | 2001-02-27 | 2002-10-02 | 中国林业科学研究院林产化学工业研究所 | Process for preparing outdoor weathe resistance epoxy resin |
| CN1793224A (en) * | 2005-12-20 | 2006-06-28 | 东莞理工学院 | Composite of non-halogen flame retarded type epoxy resin and semi-solidified sheet containing same composite and copper foil clad laminated board |
Non-Patent Citations (4)
| Title |
|---|
| 余彩莉，张发爱，陈林.松香丙烯酸加成物的溴化.《桂林工学院学报》.2007,第27卷(第4期),565-568. * |
| 孙惠久,赵世民.松香的溴化及其生成物阻燃性的研究.《西北轻工业学院学报》.2000,第18卷(第3期),93-97. * |
| 李佶辉，哈成勇.松香改性的研究进展.《天然产物研究与开发》.2003,第15卷(第6期),552-558. * |
| 沈敏敏,刘治猛,哈成勇,蒋欣,郝强,韦光洋.马来海松酸缩水甘油酯的合成.《广州化学》.2001,第26卷(第2期),21-26. * |
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