CN103848870A - Preparation method of N-P intumescent oily fiberglass reinforced plastic flame retardant - Google Patents
Preparation method of N-P intumescent oily fiberglass reinforced plastic flame retardant Download PDFInfo
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- CN103848870A CN103848870A CN201410100015.5A CN201410100015A CN103848870A CN 103848870 A CN103848870 A CN 103848870A CN 201410100015 A CN201410100015 A CN 201410100015A CN 103848870 A CN103848870 A CN 103848870A
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Abstract
The invention discloses a preparation method of an N-P intumescent oily fiberglass reinforced plastic flame retardant. The preparation method comprises the following steps: 1) adding strong phosphoric acid to a reaction kettle, heating and stirring, controlling temperature at 30-70 DEG C, adding citric acid as a catalyst, adding polylol after the catalyst is dissolved, warming up, and implementing an esterification reaction for 1-2 hours at 100-150 DEG C; 2) adding the catalyst after the esterification reaction, adding urea after the catalyst is dissolved, warming up, carrying out a condensation reaction for 1.5-2.0 hours at 160-220 DEG C and cooling to obtain a light yellow solid; 3) adding water to the light yellow solid in a mass ratio of (15-20):100, heating and melting to obtain the brown oily liquid flame retardant. The preparation method disclosed by the invention is simple in synthesis process, low in raw material cost, wide in source, environment-friendly and easy to realize industrial production.
Description
Technical field
The present invention relates to the preparation method of fire retardant, specifically, is a kind of preparation method of N-P swelling property oily glass reinforced plastic fire retardant
Background technology
Organic halogenated flame retardant is due to too serious to the pollution of environment, form the important hazard factor of haze weather, it is focus that BACN becomes people's research, wherein dimethyl methyl phosphonate (DMMP) is that a kind of novel phosphorus is environmental protection fire retarding agent, the advantage such as flame retardant resistance, water-soluble and consistency are good, therefore, be subject to people's favor, be widely used in the fire-retardant finish of various macromolecular materials.Goods have added after DMMP, and self-extinguishing, plasticity, lower temperature resistance, UV stable, drainage and static resistance etc. are all better than other common fire retardants.But at present at home, the suitability for industrialized production of DMMP is not well realized, its reason is mainly that synthesis condition and technique are too harsh, and raw materials cost is too high.About synthesizing of DMMP, at present main synthesis path has three kinds:
1, with HP (O) (OCH
3)
2for raw material synthesizes
These two kinds of synthesis paths are all used Poisons prussiate in reaction process, not only unfavorable to operating and protecting, but also make the very good difficulty of purification of product.
2, pyrolysis method
MeO
2CCI+P(OCH
3)
3——MeO
2P(O)Me
This kind of method steps is various, complex process, and product separation difficulty, and yield is lower, is difficult to realize industrialization.
3, isomerization method
The reaction mechanism of the synthetic DMMP of isomerization method is to be reacted by the synthetic phosphorus carbon bond Michaelis-Arbuzov of phosphite, familiar Phosphorus trichloride.In Phosphorus trichloride reaction process, need to use methyl iodide as catalyzer, but because the toxicity of methyl iodide is larger, and cost is higher, has once limited greatly the suitability for industrialized production of this kind of method.
Summary of the invention
Technical problem to be solved by this invention is, a kind of preparation method of halogen-free flame retardants N-P swelling property oily glass reinforced plastic fire retardant is provided, adopt a kind of new preparation technology and raw material, this technique does not have waste water, waste residue, exhaust gas emission, technique is simple to operation, and raw material is inexpensive, has greatly saved production cost, production process environmental protection, is conducive to suitability for industrialized production.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of N-P swelling property oily glass reinforced plastic fire retardant, comprises the following steps:
1) in reactor, add strong phosphoric acid, heat and stir, temperature is controlled at 30 DEG C-70 DEG C, adds catalyzer citric acid, adds polyvalent alcohol after catalyst dissolution again, heats up, and carries out esterification at 100 DEG C-150 DEG C, reaction 1-2 hour;
2) esterification adds catalyzer after completing, and adds urea after catalyst dissolution, heats up, and carries out condensation reaction at 160 DEG C-220 DEG C, and reaction 1.5-2.0 hour, obtains faint yellow solid after cooling;
3) be 100:(15-20 according to faint yellow solid with quality ratio) add water, heating and melting to obtain the liquid combustion inhibitor of sorrel oily.
The consumption mol ratio of described strong phosphoric acid, polyvalent alcohol, urea is 2.0-2.5:1:2.0-3.0.
Described polyvalent alcohol is the one in tetramethylolmethane, dipentaerythritol, tripentaerythritol or neopentyl glycol.
The consumption of the catalyzer citric acid of described step 1) is the 1%-3% of esterification total mass.
Described step 2) in catalyzer be the one in Phenylsulfonic acid, p-methyl benzenesulfonic acid or Witco 1298 Soft Acid, its consumption is the 0.20%-0.3% of total mass that participates in reactive material.
The invention has the beneficial effects as follows: the present invention uses raw material cheap and easy to get, and cost is low, yield is high is applicable to scale operation; Synthesis condition and technique are simple, are beneficial to operation and protection, and production process environmental protection, easily realizes suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
The preparation method of N-P swelling property oily glass reinforced plastic fire retardant of the present invention, comprises the following steps:
1) in reactor, add strong phosphoric acid, heat and stir, temperature is controlled at 30 DEG C-70 DEG C, adds catalyzer citric acid, adds polyvalent alcohol after catalyst dissolution again, heats up, and carries out esterification at 100 DEG C-150 DEG C, reaction 1-2 hour;
2) esterification adds catalyzer after completing, and adds urea after catalyst dissolution, heats up, and carries out condensation reaction at 160 DEG C-220 DEG C, and reaction 1.5-2.0 hour, obtains faint yellow solid after cooling;
3) be 100:(15-20 according to faint yellow solid with quality ratio) add water, heating and melting to obtain the liquid combustion inhibitor of sorrel oily.
The consumption mol ratio of described strong phosphoric acid, polyvalent alcohol, urea is 2.0-2.5:1:2.0-3.0.
Described polyvalent alcohol is the one in tetramethylolmethane, dipentaerythritol, tripentaerythritol or neopentyl glycol.
The consumption of the catalyzer citric acid of described step 1) is the 1%-3% of esterification total mass.
Described step 2) in catalyzer be the one in Phenylsulfonic acid, p-methyl benzenesulfonic acid or Witco 1298 Soft Acid, its consumption is the 0.20%-0.3% of total mass that participates in reactive material.
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with example, but content of the present invention is not only confined to example below.Following embodiment and application example reagent used is analytical pure.
Embodiment 1
In there-necked flask, add phosphoric acid 231g(mass percent concentration 85%), there-necked flask is put into oil bath, start stirring, temperature is controlled at 30 DEG C, adds catalyzer citric acid 3.75g, and citric acid dissolves completely, and in this process, reaction soln is light yellow; Add tetramethylolmethane 144g again, put into oil bath and carry out esterification, temperature is controlled at 110 DEG C, reacts 1 hour, after esterification completes; 2) add catalyzer Phenylsulfonic acid 1.335g, add urea 120.0g after catalyst dissolution, oil bath heats up, and temperature is controlled at 160 DEG C, reacts 1.5 hours, after product is cooling, is faint yellow solid; 3) in faint yellow solid, add water, solid is with quality than being 100:15, and heating and melting becomes the liquid combustion inhibitor of sorrel oily; 4) by mass percentage, the liquid combustion inhibitor of 10% sorrel oily is mixed compatible with unsaturated lipid 196, solidifying agent methylethyl ketone peroxide two formicesters, promotor xylidine, be prepared into glass reinforced plastic plank, test according to GB16403-1966.Without black smoke, play carbon bubble, fire extinguishing is fast, and burning area is little, the results are shown in Table 1.
Embodiment 2
In there-necked flask, add phosphoric acid 254g(mass percent concentration 85%), there-necked flask is put into oil bath, start stirring, temperature is controlled at 40 DEG C, adds catalyzer citric acid 5.97g, and citric acid dissolves completely, and in this process, reaction soln is light yellow; Add 144 grams of tetramethylolmethanes again, put into oil bath and carry out esterification, temperature is controlled at 130 DEG C, reacts 1 hour, after esterification completes; 2) add catalyzer Witco 1298 Soft Acid 1.500g, add urea 138g after catalyst dissolution, oil bath heats up, and temperature is controlled at 180 DEG C, reacts 2.0 hours, after product is cooling, is faint yellow solid; 3) according to adding water in the faint yellow solid of above-mentioned steps 2 gained, solid is with quality than being 100:18, and heating and melting becomes the liquid combustion inhibitor of sorrel oily; 4) by mass percentage, the liquid combustion inhibitor of 10% sorrel oily is mixed with unsaturated lipid 191, solidifying agent benzoyl peroxide, promotor peroxide ring ethyl ketone and add alkali-free fiberglass cloth to make glass epoxy to test according to GB16403-1966.Without black smoke, play carbon bubble, fire extinguishing is fast, and burning area is little, the results are shown in Table 1.
Embodiment 3
In there-necked flask, add phosphoric acid 288g(mass percent concentration 85%), there-necked flask is put into oil bath, start stirring, temperature is controlled at 60 DEG C, adds catalyzer citric acid 8.64g, and citric acid dissolves completely, and in this process, reaction soln is light yellow; Add 144 grams of tetramethylolmethanes again, put into oil bath and carry out esterification, temperature is controlled at 130 DEG C, reacts 1.5 hours, after esterification completes; 2) add catalyzer Witco 1298 Soft Acid 1.51g, add urea 150g after catalyst dissolution, oil bath heats up, and temperature is controlled at 190 DEG C, reacts 2.0 hours, after product is cooling, is faint yellow solid; 3) according to adding water in the faint yellow solid of above-mentioned steps 2 gained, solid is with quality than being 100:20, and heating and melting becomes the liquid combustion inhibitor of sorrel oily; 4) by mass percentage, the liquid combustion inhibitor of 10% sorrel oily is mixed with unsaturated lipid 191, solidifying agent benzoyl peroxide, promotor peroxide ring ethyl ketone and add alkali-free fiberglass cloth to make glass epoxy to test according to GB16403-1966.Without black smoke, play carbon bubble, fire extinguishing is fast, and burning area is little, the results are shown in Table 1.
Table 1 adds oily fire retardant combustion efficacy prepared by the present invention
Combustion experiment condition: alcohol blast burner, flame temperature reaches 960 left and right, lights after glass epoxy (fire retardant addition is 10%) 30S, leaves flame.
Above-described embodiment is only for illustrating technological thought of the present invention and feature, its object is to make those skilled in the art can understand content of the present invention and implement according to this, can not only limit the scope of the claims of the present invention with the present embodiment, be equal variation or the modification that all disclosed spirit is done, still drop in the scope of the claims of the present invention.
Claims (5)
1. a preparation method for N-P swelling property oily glass reinforced plastic fire retardant, is characterized in that, comprises the following steps:
1) in reactor, add strong phosphoric acid, heat and stir, temperature is controlled at 30 DEG C-70 DEG C, adds catalyzer citric acid, adds polyvalent alcohol after catalyst dissolution again, heats up, and carries out esterification at 100 DEG C-150 DEG C, reaction 1-2 hour;
2) esterification adds catalyzer after completing, and adds urea after catalyst dissolution, heats up, and carries out condensation reaction at 160 DEG C-220 DEG C, and reaction 1.5-2.0 hour, obtains faint yellow solid after cooling;
3) be 100:(15-20 according to faint yellow solid with quality ratio) add water, heating and melting to obtain the liquid combustion inhibitor of sorrel oily.
2. the preparation method of N-P swelling property oily glass reinforced plastic fire retardant according to claim 1, is characterized in that, the consumption mol ratio of described strong phosphoric acid, polyvalent alcohol, urea is 2.0-2.5:1:2.0-3.0.
3. the preparation method of N-P swelling property oily glass reinforced plastic fire retardant according to claim 1, is characterized in that, described polyvalent alcohol is the one in tetramethylolmethane, dipentaerythritol, tripentaerythritol or neopentyl glycol.
4. the preparation method of N-P swelling property oily glass reinforced plastic fire retardant according to claim 1, is characterized in that, the consumption of the catalyzer citric acid of described step 1) is the 1%-3% of esterification total mass.
5. the preparation method of N-P swelling property oily glass reinforced plastic fire retardant according to claim 1, it is characterized in that, described step 2) in catalyzer be the one in Phenylsulfonic acid, p-methyl benzenesulfonic acid or Witco 1298 Soft Acid, its consumption is the 0.20%-0.3% of total mass that participates in reactive material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410100015.5A CN103848870A (en) | 2014-03-18 | 2014-03-18 | Preparation method of N-P intumescent oily fiberglass reinforced plastic flame retardant |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422772A (en) * | 2012-05-24 | 2013-12-04 | 中国林业科学研究院木材工业研究所 | Wood-plastic composite section and preparation method thereof |
-
2014
- 2014-03-18 CN CN201410100015.5A patent/CN103848870A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422772A (en) * | 2012-05-24 | 2013-12-04 | 中国林业科学研究院木材工业研究所 | Wood-plastic composite section and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 江进学: ""氮磷基阻燃剂处理木材的特性研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王勋章 等: ""无卤阻燃剂季戊四醇双磷酸蜜胺盐的合成与应用"", 《化工科技》 * |
| 赵辉等: ""二季戊四醇磷酸酯的合成、表征及阻燃性能测试"", 《化学研究与应用》 * |
| 高明 等: ""含季戊四醇二磷酸酯三聚氰胺-尿醛树脂盐环氧树脂的阻燃性能"", 《过程工程学报》 * |
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