CN103224599A - Preparation method of resorcinol formaldehyde resin-based macromolecular fire retardant - Google Patents
Preparation method of resorcinol formaldehyde resin-based macromolecular fire retardant Download PDFInfo
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- CN103224599A CN103224599A CN2013100200573A CN201310020057A CN103224599A CN 103224599 A CN103224599 A CN 103224599A CN 2013100200573 A CN2013100200573 A CN 2013100200573A CN 201310020057 A CN201310020057 A CN 201310020057A CN 103224599 A CN103224599 A CN 103224599A
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Abstract
The invention discloses a preparation method of a resorcinol formaldehyde resin-based macromolecular fire retardant. The preparation method comprises that resorcinol formaldehyde resin and phosphorous oxychloride are synthesized into an intermediate and then the intermediate and melamine are synthesized into the resorcinol formaldehyde resin-based macromolecular fire retardant which is a macromolecular intumescent fire retardant. The macromolecular intumescent fire retardant has good expansion flame retardation performances to epoxy resin polymers. Phosphor and carbon are introduced into a polymer so that the macromolecular intumescent fire retardant is synthesized an thus fire retardant stability and fire retardant compatibility with a polymer are improved. In preparation of the resorcinol formaldehyde resin-based macromolecular fire retardant, through treatment at two different temperatures, a catalyst is avoided; a reaction temperature is reduced; reaction time is shortened; and a preparation cost is reduced. The preparation method has the advantages of cheap raw materials, short reaction time, and simple and convenient separation.
Description
Technical field
The invention belongs to flame retardant area, be specifically related to a kind of preparation method of the macromole fire retardant based on resorcinol formaldehyde resin.
Background technology
Expansion day by day along with the macromolecular material range of application, the reinforcement day by day of global safety environmental consciousness, people are more and more higher to the fire-retardant requirement of macromolecule material product, and the environment friendly flame retardant of Halogen, low cigarette, low toxicity, high heat resistance has become the target that people pursue.In existing fire retardant, traditional halogenated flame retardant has the flame retarding efficiency height, the material fundamental property is influenced advantages such as little, but it can produce volume of smoke, corrosive gases and some toxic substances in thermolysis and burning, the serious harm human health, and environment polluted.Therefore, halogenated flame retardant is substituted by the green fire retardant of Halogen just gradually.The small molecules phosphonium flame retardant is because of its Halogen, low cigarette, non-corrosiveness gas are emitted and had fewer environmental impacts.But the small molecules phosphonium flame retardant exists, problems such as volatility big, poor heat resistance poor with the polymer phase capacitive, thereby physics, machinery, the flame retardant properties of flame-proof composite material are brought disadvantageous effect.
In order to overcome the above-mentioned shortcoming of fire retardant, the scientific research personnel is applied to micro-capsule package technology the modification aspect of fire retardant, promptly with natural or synthesized polymer material fire retardant being rolled into diameter is micron-sized capsule, thereby improves the water tolerance and the consistency of fire retardant.For example: Chinese invention patent CN101812305A discloses a kind of three-source integrated microcapsule intumescent flame retardant and preparation method thereof, this fire retardant collection acid source, the gentle one that comes from charcoal source, but there are problems such as " technology controlling and process difficulty ", " need high-speed stirring, power consumption is high ", " cost is higher " in micro-encapsulation technology.The low polyphosphate based flame retardant is to study more novel phosphorus flame retardant at present, wherein Resorcinol two (diphenyl phosphoesters) (RDP), Resorcinol two (diphenyl phosphoester) (RDP), dihydroxyphenyl propane two (diphenyl phosphoester) (BDP), bisphenol S two (diphenyl phosphoester) (BSDP) and bisphenol-ap two (diphenyl phosphoester) (BAPDP) receive much concern (Huang is conquered east. the low polyphosphate fire retardant synthetic with use [D]. tutor: Yang Jinfei. Nanjing Normal University, 2007), but these fire retardants are in 200-250 ℃ of beginning cracking, poor heat stability.The fluorine element that induces one in polyphosphoric acid vinegar can improve the thermostability and the flame retardant resistance of fire retardant, but the toxicity height (Ou Rongqing, all political affairs Mao. the present situation and the progress of phosphoric acid ester and poly phosphate based flame retardant. fire-retardant science and technology, 2004, (1): 14-15).Employing coats trimeric cyanamide polyphosphate (MPP) fire retarding epoxide resin with the KH-560 silane coupling agent, and effect is better, but fire retardant, the big (Yin Jinjie of hardener dose, Li Ning, open tree. the development of fire retarding epoxide resin sizing agent [J]. chemical and bonding, 2008,02:24-26).Propositions such as Zhang Min prepare the macromole fire retardant with the PET degraded product, and environmental friendliness has application promise in clinical practice.(open synthetic fire retardant of polyphosphate of quick .PET degraded and flame retardant properties research [D] thereof. tutor: Yang Feng. Wuhan Textile University, 2011).That the research and development of phosphoric acid vinegar based flame retardant is used is good to thermostability height, intermiscibility, high-molecular weight fire retardant direction develops.Resorcinol formaldehyde resin is widely used in the tamanori field, but utilizes this resins macromole fire retardant not appear in the newspapers.
Summary of the invention
For addressing the above problem, the purpose of this invention is to provide a kind of preparation method of the macromole fire retardant based on resorcinol formaldehyde resin, preparation technology is simple, stable, obtains the good phosphorus nitrogen of a kind of polymer-polymer miscibility synergistic macromole type halogen-free expansion fire retardant.
The apprizing system of sample treatment plant reaches above-mentioned technique effect for realizing above-mentioned technical purpose, and the present invention is achieved through the following technical solutions:
A kind of preparation method of the macromole fire retardant based on resorcinol formaldehyde resin may further comprise the steps:
Step 1) adds resorcinol formaldehyde resin and solvent in there-necked flask, the room temperature lower magnetic force stirs resorcinol formaldehyde resin is dissolved fully, be made into 0.2-0.5 mol/L solution A, in solution A, slowly drip phosphorus oxychloride and obtain solution B, solution B slowly is warmed up to 50-70 ℃, reaction 2-3h, progressively elevated temperature reacts 5-8h again to 75-85 ℃, after reaction finishes, cooling, vacuum filtration, use again solvent wash 2-3 time, vacuum-drying obtains brown xanchromatic solid to constant weight under 50-70 ℃ of condition, is intermediate;
Step 2) described intermediate is dissolved in N, dinethylformamide DMF is mixed with the solution C of 0.2-0.5 mol/L, according to the mol ratio intermediate: trimeric cyanamide=1:1 adds trimeric cyanamide, and elevated temperature is to 100-115 ℃, isothermal reaction 4-7h, reaction finishes postcooling, vacuum filtration is washed 2-3 time with DMF and methylene dichloride respectively, puts into baking oven, dry 24h under 105 ℃ of conditions, obtain the macromole fire retardant.
Further, the amount of substance of resorcinol formaldehyde resin described in the step 1) is 0.05mol, in the C7H6O2 structural unit.
Further, solvent described in the step 1) is selected from methylene dichloride, trichloromethane, 1, a kind of in the 2-ethylene dichloride.
Further, resorcinol formaldehyde resin described in the step 1) and described phosphorus oxychloride mol ratio are 1:1.5-2.5.
The invention has the beneficial effects as follows:
1, the present invention introduces synthetic macromolecule expansion type flame retardant in the same macromolecular structure with phosphorus, carbon, improved fire retardant stability and with high molecular consistency;
2, the present invention by the processing of two kinds of differing tempss, make reaction not need to add catalyzer, and temperature of reaction is lower when the macromole fire retardant of preparation resorcinol formaldehyde resin, and the reaction times is shorter, thereby has reduced preparation cost.
3, the present invention has advantages such as raw material is cheap, the reaction times short, separation is easy.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Description of drawings
Fig. 1 is the schematic flow sheet of preparation macromole expanding fire retardant among the embodiment one;
Fig. 2 is the infrared analysis figure of embodiment one gained macromole expanding fire retardant;
Fig. 3 is the TG curve of macromole fire retardant, Resins, epoxy, and (1) is Resins, epoxy, and (2) are fire retardant;
Fig. 4 is the 1H NMR collection of illustrative plates of macromole fire retardant;
Fig. 5 is the volumetric expansion design sketch of macromole fire retardant Resins, epoxy.
Embodiment
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
Embodiment one:
Referring to shown in Figure 1, a kind of preparation method of the macromole fire retardant based on resorcinol formaldehyde resin may further comprise the steps:
Step 1) adds 6.10g(0.05mol in the there-necked flask of 250ml, with C
7H
6O
2The structural unit meter, 122g/mol) resorcinol formaldehyde resin and 150ml methylene dichloride, under magnetic stirrer, treat that resorcinol formaldehyde resin is dispersed in the methylene dichloride, beginning slowly drips 15.40g (0.10mol) phosphorus oxychloride, dropwise the back and earlier slowly be warmed up to 60 ℃, react 2h under 60 ℃ of conditions, progressively elevated temperature to 80 ℃ reacts 7h again.After reaction finishes, cooling, vacuum filtration is used washed with dichloromethane 2-3 time again, and vacuum-drying obtains brown xanchromatic intermediate to constant weight under 60 ℃ of conditions, obtains the product of 9.83g, productive rate 65.08%.
Step 2) the intermediate 4.8g (0.02mol) that obtains is dissolved in the DMF of 100ml, treats that solid dispersed evenly adds 2.52g (0.02mol) trimeric cyanamide in the back, elevated temperature to 110 ℃.Isothermal reaction 6h, reaction finishes postcooling, and vacuum filtration is used N respectively, and dinethylformamide and methylene dichloride are washed 2-3 time, put into baking oven, dry 24h under 105 ℃ of conditions, obtain macromole fire retardant 3.73g, productive rate 50.93%.
Table 1 is that n (resorcinol formaldehyde resin): n (phosphorus oxychloride) is than the not influence of centering mesosome productive rate simultaneously, as seen proportioning raw materials is very big to the influence of reaction, the consumption of phosphorus oxychloride is very few, then the resorcinol formaldehyde resin reaction not exclusively, influence yield, cause the waste of raw material, phosphorus oxychloride is too much, though reaction is fast, the aftertreatment segregational load increases and uneconomical.
| Numbering | N (resorcinol formaldehyde resin): n (phosphorus oxychloride) | Productive rate/% |
| 1 | 1:1 | 32.53 |
| 2 | 1:1.5 | 56.89 |
| 3 | 1:2 | 65.08 |
| 4 | 1:2.5 | 60.44 |
| 5 | 1:3 | 58.32 |
Table 1
Table 2 is n (intermediate product): n (trimeric cyanamide) than not simultaneously to the influence of macromole fire retardant productive rate.
| Numbering | N (intermediate product): n (trimeric cyanamide) | Productive rate/% |
| 1 | 3:1 | 18.24 |
| 2 | 2:1 | 25.87 |
| 3 | 1:1 | 50.93 |
| 4 | 1:1.5 | 70.73 |
| 5 | 1:2 | 69.84 |
Table 2
Referring to shown in Figure 2,3118 cm
-1Be the stretching vibration of N-H key, 1676 cm
-1, 1499 cm
-1Be the skeletal vibration of C-C on the phenyl ring, 13647cm
-1Be the stretching vibration of P=O, 1166 cm
-1Be the absorption peak of Ar – O – P, 778 cm
-1Being the charateristic avsorption band of P-N-C, is target product by the provable synthetic product of above infared spectrum.
Referring to shown in Figure 3, Resins, epoxy (1) fs, obvious thermal weight loss was positioned at 350 ℃, and the obvious thermal weight loss of subordinate phase is positioned at 550 ℃; Macromole fire retardant (2) fs, obvious thermal weight loss was positioned at 300 ℃, and the obvious thermal weight loss of subordinate phase is positioned at 420-530 ℃.Thermogravimetric analysis is the result show, the macromole fire retardant is starkly lower than about 50 ℃ of Resins, epoxy in fs thermal weight loss temperature, and subordinate phase is lower than about 130 ℃ of Resins, epoxy.Simultaneously as can be known, the macromole fire retardant is in better heat stability more than 600 ℃, and residual heavy in the time of 700 ℃ is about 40%, is higher than Resins, epoxy far away, illustrates that the macromole fire retardant has good flame retardancy.Can predict macromole fire retardant fire retarding epoxide resin preferably.
Referring to shown in Figure 4, wherein δ=2.496-3.010ppm place is-characteristic peak of CH2, δ=3.380ppm place is-characteristic peak of OH, δ=5.951ppm place is the characteristic peak of H adjacent with the P-O-C key on the phenyl ring, δ=7.482-7.578ppm place is the characteristic peak of H on the phenyl ring, and δ=9.543-9.551ppm place is-NH
2 +Characteristic peak.
Embodiment two:
Step 1) adds 6.10g(0.05mol in the there-necked flask of 250ml) resorcinol formaldehyde resin and 150ml methylene dichloride, under magnetic stirrer, treat that resorcinol formaldehyde resin is dispersed in the methylene dichloride, beginning slowly drips 15.40g (0.10mol) phosphorus oxychloride, dropwise the back and slowly be warmed up to 60 ℃ earlier, react 2h under 60 ℃ of conditions, progressively elevated temperature to 80 ℃ reacts 7h again.After reaction finishes, cooling, vacuum filtration is used washed with dichloromethane 2-3 time again, and vacuum-drying obtains brown xanchromatic solid to constant weight under 60 ℃ of conditions, obtains the product of 9.83g, productive rate 71.23%.
Step 2) the solid 4.8g (0.02mol) that obtains is dissolved in the N of 100ml, dinethylformamide treats that solid dispersed evenly adds 2.52g (0.02mol) trimeric cyanamide in the back, elevated temperature to 110 ℃.Isothermal reaction 6h, reaction finishes postcooling, and vacuum filtration is used N respectively, and dinethylformamide and methylene dichloride are washed 2-3 time, put into baking oven, dry 24h under 105 ℃ of conditions.
Embodiment three: the flame retardant properties of test macromole fire retardant
Macromole fire retardant with embodiment one is that 5%-30% joins in the E-44 Resins, epoxy by massfraction respectively, add an amount of solidifying agent EDA after stirring again and be prepared into standard test specimen, sample is carried out limiting oxygen index(LOI) (LOI) test according to GB/T2406-2009 plastics oxygen index testing method.
The result is as shown in table 3 below, and the limit-in-mean oxygen index (LOI) of blank Resins, epoxy sample is 19%, and the limiting oxygen index(LOI) (LOI) of Resins, epoxy behind the macromole fire retardant sees Table 3.As shown in table 3, when add fire retardant in Resins, epoxy after, the oxygen index value of Resins, epoxy raises along with the increase of the amount of fire retardant, and oxygen index value has reached 32% when addition is 30%, and the product that generated fire retarding epoxide resin effectively is described.
| Numbering | Fire retardant addition/% | LOI/% |
| 1 | 0 | 19 |
| 2 | 5 | 22 |
| 3 | 10 | 23 |
| 4 | 15 | 26 |
| 5 | 20 | 30 |
| 6 | 25 | 31 |
| 7 | 30 | 32 |
Table 3
Referring to shown in Figure 5, left side figure is the pattern after the fire retarding epoxide resin that added the macromole fire retardant burns, right figure is the pattern after the Resins, epoxy burning, compare the two as can be known, the Resins, epoxy that adds the macromole fire retardant obviously expands after burning, volume than pure epoxy resin has expanded 18 times approximately, illustrates that the expandable flame retardant of fire retardant is respond well.
The above only for the preferred embodiment of invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. the preparation method based on the macromole fire retardant of resorcinol formaldehyde resin is characterized in that, may further comprise the steps:
Step 1) adds resorcinol formaldehyde resin and solvent in there-necked flask, the room temperature lower magnetic force stirs resorcinol formaldehyde resin is dissolved fully, be made into 0.2-0.5 mol/L solution A, in solution A, slowly drip phosphorus oxychloride and obtain solution B, solution B slowly is warmed up to 50-70 ℃, reaction 2-3h, progressively elevated temperature reacts 5-8h again to 75-85 ℃, after reaction finishes, cooling, vacuum filtration, use again solvent wash 2-3 time, vacuum-drying obtains brown xanchromatic solid to constant weight under 50-70 ℃ of condition, is intermediate;
Step 2) described intermediate is dissolved in N, dinethylformamide DMF is mixed with the solution C of 0.2-0.5 mol/L, according to the mol ratio intermediate: trimeric cyanamide=1:1 adds trimeric cyanamide, and elevated temperature is to 100-115 ℃, isothermal reaction 4-7h, reaction finishes postcooling, vacuum filtration is washed 2-3 time with DMF and methylene dichloride respectively, puts into baking oven, dry 24h under 105 ℃ of conditions, obtain the macromole fire retardant.
2. the preparation method of the macromole fire retardant based on resorcinol formaldehyde resin according to claim 1, it is characterized in that: the amount of substance of resorcinol formaldehyde resin described in the step 1) is 0.05mol, with C
7H
6O
2The structural unit meter.
3. the preparation method of the macromole fire retardant based on resorcinol formaldehyde resin according to claim 1, it is characterized in that: solvent described in the step 1) is selected from methylene dichloride, trichloromethane, 1, a kind of in the 2-ethylene dichloride.
4. the preparation method of the macromole fire retardant based on resorcinol formaldehyde resin according to claim 1, it is characterized in that: resorcinol formaldehyde resin described in the step 1) and described phosphorus oxychloride mol ratio are 1:1.5-2.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327304A (en) * | 2014-10-27 | 2015-02-04 | 沈阳化工大学 | Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5075413A (en) * | 1989-02-07 | 1991-12-24 | Indspec Chemical Corporation | Resorcinol-modified phenolic resin binder for reinforced plastics |
| CN1995085A (en) * | 2006-10-22 | 2007-07-11 | 李超 | Synthesis process of phosphorous-containing phenolic resin |
| CN102040630A (en) * | 2010-12-07 | 2011-05-04 | 南昌航空大学 | Preparation method of three-in-one acrylic acid phosphoric melamine expansion flame retardant oligomer |
| CN102276767A (en) * | 2011-06-24 | 2011-12-14 | 苏州科技学院 | Method for preparing macromolecular halogen-free flame retardant by utilizing waste polystyrene |
-
2013
- 2013-01-21 CN CN2013100200573A patent/CN103224599A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5075413A (en) * | 1989-02-07 | 1991-12-24 | Indspec Chemical Corporation | Resorcinol-modified phenolic resin binder for reinforced plastics |
| CN1995085A (en) * | 2006-10-22 | 2007-07-11 | 李超 | Synthesis process of phosphorous-containing phenolic resin |
| CN102040630A (en) * | 2010-12-07 | 2011-05-04 | 南昌航空大学 | Preparation method of three-in-one acrylic acid phosphoric melamine expansion flame retardant oligomer |
| CN102276767A (en) * | 2011-06-24 | 2011-12-14 | 苏州科技学院 | Method for preparing macromolecular halogen-free flame retardant by utilizing waste polystyrene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327304A (en) * | 2014-10-27 | 2015-02-04 | 沈阳化工大学 | Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant |
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Application publication date: 20130731 |