CN104389165A - Preparation method for multi-component intumescent flame retardant for acrylic fabric - Google Patents
Preparation method for multi-component intumescent flame retardant for acrylic fabric Download PDFInfo
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- CN104389165A CN104389165A CN201410569016.4A CN201410569016A CN104389165A CN 104389165 A CN104389165 A CN 104389165A CN 201410569016 A CN201410569016 A CN 201410569016A CN 104389165 A CN104389165 A CN 104389165A
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Abstract
The invention relates to a preparation method for a multi-component intumescent flame retardant for acrylic fabric, and belongs to the technical field of synthesis. The synthesis process comprises the two steps: firstly, pentaerythritol, phosphoric acid, a catalyst and a water-carrying agent are subjected to the azeotropic reaction to obtain pentaerythritol phosphate; then, the pentaerythritol phosphate and alkylol amine are subjected to the azeotropic reaction for esterification and salifying, or the pentaerythritol phosphate and melamine are directly subjected to salifying, and finally, flame retardants with different components are respectively obtained. The multi-component intumescent flame retardant prepared by the method is good in water solubility, convenient to use and excellent in flame retardant property, and belongs to an environment-friendly flame retardant which is non-poisonous, low-smoke and efficient. The synthesis process of the flame retardant is simple, raw materials are low in price and easy to obtain, the water-carrying agent can be recycled, organic pollution is avoided, the production efficiency is high, the energy consumption is low, and the industrial implementation is facilitated.
Description
Technical field
The invention belongs to synthesis technical field, be specifically related to the preparation method of a class acrylic fabric multicomponent expansion type flame retardant.
Background technology
Acrylic fibers are one of main synthetic fiber kinds, and current China has become the first in the world acrylic fiber production process big country.The performances such as it is fluffy, curling, soft are similar to wool, have the woolly feel of class and warmth retention property.Fibre strength and the anti-wear performance of acrylic fibers are all better than wool.In addition, acrylic fabric is easily washed easily dry, and nursing is simple, has light resistance, weather fastness, fungus resistance and excellent chemical stability.But meanwhile, acrylic fibers belong to inflammability fiber, and limited oxygen index is only 18, belong to minimum in synthetic fiber, during burning, release the larger cyanide of toxicity and ammonia etc.Therefore, the research and development of flame-retardant acrylic fibre are very necessary.At present, the flame-retardant acrylic fibre of domestic and international trial production, general is all adopt halogenated flame retardant, in order to reduce the speed of acrylic fiber propagation of flame and burning, but halogen containing flame-retardant produces fire-retardant eyeball synthetic fibre, can pollute working environment, and burn time formed to harm greatly poisonous, be corrosive gas, thus develop the non-halogenated flame retardant of low cigarette, low toxicity, be of great immediate significance.
The composite flame-retardant agent that it is essential core composition that expansion type flame retardant typically refers to phosphorus, nitrogen, carbon, it is generally made up of three parts: carbonized agent (charcoal source), charing catalyst (acid source), swelling agent (source of the gas).When being heated with its fire-retardant polymer, certain thickness porous layer of charcoal can be formed on its surface, this layer of charcoal has heat insulation, oxygen barrier, presses down the function of cigarette and anti-molten drop, thus plays good fire retardation, and meets the development trend requiring the few cigarette of fire retardant, low toxicity now.
The expansion type flame retardant of current suitability for industrialized production adopts phosphorus oxychloride to be acid source mostly, and polyalcohol is carbon source, and melamine is nitrogenous source, as the preparation of pentaerythritol diphosphonate melamine salt.But, be that acid source prepares polyol ester phosphate and derivative thereof with phosphorus oxychloride, relate to the industrial production problems such as phosphorus oxychloride danger, toxic, make the accumulating of raw material and the enforcement of reaction process relate to more safety problem; And phosphorus oxychloride and polyhydric alcohol react the hydrogen chloride of releasing macro-corrosion, the loss of equipment and exhaust-gas treatment are also the problems that can not be ignored.
The scholar such as domestic king's medal, Wu Zhiping, Li Fengying, Zheng Hui, Li Shuhong, and I adopts polyphosphoric acids or phosphoric acid to be that acid source prepares polyol ester phosphate and derivative thereof, achieves good flame retardant effect.
In sum, the exploitation of acrylic fabric expansion type flame retardant has sufficient necessity; Tradition phosphorus oxychloride is that the preparation technology of the expansion type flame retardant of acid source exists certain safety problem; Phosphoric acid is that the expansion type flame retardant of acid source has certain Research foundation, but is the product of addition type, cannot carry out acrylic fibers Final finishing.
Summary of the invention
The object of this invention is to provide the preparation method of acrylic fabric multicomponent expansion type flame retardant.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, preparation process is divided into two steps:
(1) first step: pentaerythrite, phosphoric acid, catalyst, water entrainer are added in reactor, azeotropic reaction 4-8h, after having reacted, excessive phosphoric acid and water entrainer are removed in decompression distillation, obtain pale yellow or brown viscous liquid product A;
(2) second step: add hydramine, water entrainer in the reactor of above-mentioned product A, azeotropic reaction 3.5-5.5h, after having reacted, water entrainer is removed in decompression distillation, obtains brown viscous liquid product B; Or in the reactor of above-mentioned product A, add a small amount of melamine, Shao Liangshui, 75-95 DEG C reaction, reaction 0.5-2h, after having reacted, filter out unreacted melamine, decompression distillation is anhydrated, and obtains colourless viscous liquid product B; B is target product, multicomponent expansion type flame retardant.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, the second step of described building-up process is add hydramine, water entrainer in the reactor of product A, and azeotropic reaction 3-5h, after having reacted, water entrainer is removed in decompression distillation, obtains brown viscous liquid product B; Or in the reactor of above-mentioned product A, adding a small amount of melamine, Shao Liangshui, 75-95 DEG C reaction, reaction 0.5-3h, after having reacted, filter out unreacted melamine, decompression distillation is anhydrated, and obtains colourless viscous liquid product B.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, in described building-up process second step, water entrainer amount is the 50%-90% of material quality, and water entrainer is toluene.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, the catalyst in described building-up process second step is sulfuric acid, p-methyl benzenesulfonic acid, cationic ion-exchange resin etc.; The consumption of NKC-9 is the 5%-12% of material quality, and the catalytic amount such as the concentrated sulfuric acid, p-methyl benzenesulfonic acid is the 0.1%-1% of material quality.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, described in described building-up process second step, amine substance is monoethanolamine, diethanol amine, triethanolamine, melamine etc.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, the azeotropic temperature that in described building-up process second step, hydramine and pentaerythritol phosphate react is between 120-140 DEG C, and the reaction temperature of melamine and pentaerythritol phosphate is between 75-95 DEG C.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, in described building-up process second step, the mass ratio of pentaerythritol phosphate and hydramine is between 0.6-4.5, and the mass ratio of pentaerythritol phosphate and melamine is between 6-24.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, in described building-up process second step, the mass ratio of pentaerythritol phosphate and hydramine is between 0.6-4.5, and the mass ratio of pentaerythritol phosphate and melamine is between 6-24.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, in described building-up process second step, the reaction time of pentaerythritol phosphate and hydramine is between 3.5-5.5h, and the reaction time of pentaerythritol phosphate and melamine is between 0.5-2h.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, in the reaction of described building-up process second step pentaerythritol phosphate and hydramine, the dropping temperature of hydramine is between 70-120 DEG C, and the joining day is between 0-1h.
The present invention relates to the preparation method of acrylic fabric multicomponent expansion type flame retardant, materials safety is stablized, and technique is simple, and high reaction yield, does not produce organic contamination.
Fire retardant water soluble characteristic prepared by the preparation method that the present invention relates to acrylic fabric multicomponent expansion type flame retardant is good, easy to use, has good fire resistance to acrylic fibers, belongs to nontoxic, low cigarette, efficiently environment friendly flame retardant.
Detailed description of the invention
Below by embodiment, the technical scheme that the present invention relates to is described further, but not as limiting the scope of the invention.
embodiment one
Get 13.8g pentaerythrite, 48.8g phosphoric acid, 34.6g toluene joins and be equipped with in 500 mL four-hole bottles of thermometer, agitator, water knockout drum and spherical condensation tube, stir, be heated to 90 DEG C, add 0.6g p-methyl benzenesulfonic acid, and start timing, under the state of boiling, the water generate reaction and methylbenzene azeotropic steam, and separate aqueous phase refluxing toluene in water knockout drum.Reaction 5h, terminates reaction.At more than vacuum 0.09MPa, decompression distillation is carried out to reactant liquor, steam unreacted phosphoric acid (recycling), water entrainer toluene (recycling), obtain the mixture of viscous brown pentaerythritol phosphate and p-methyl benzenesulfonic acid.
Get 15.2g the said goods, 35.8g toluene, join and be equipped with in 500 mL four-hole bottles of thermometer, agitator, water knockout drum and spherical condensation tube, stir, heat to 70 DEG C after, drip 26g triethanolamine with constant pressure funnel, and start timing, 30min dropwises, azeotropic 4h, separates aqueous phase refluxing toluene in water knockout drum.After reaction terminates.At more than vacuum 0.09MPa, decompression distillation is carried out to reactant liquor, steam water entrainer toluene (recycling), obtain light brown sticky shape target product, yield 75.8%, is made into the 300g/L aqueous solution, arrange acrylic fabric, charcoal is long is 8.0cm, reaches national B1 grade standard.
embodiment two
Get 14.1 pentaerythrites, 50.1g phosphoric acid, 40.19g toluene joins and be equipped with in 500 mL four-hole bottles of thermometer, agitator, water knockout drum and spherical condensation tube, stir, be heated to 90 DEG C, add 0.7g p-methyl benzenesulfonic acid, and start timing, under the state of boiling, the water generate reaction and methylbenzene azeotropic steam, and separate aqueous phase refluxing toluene in water knockout drum.Reaction 5h, terminates reaction.At more than vacuum 0.09MPa, decompression distillation is carried out to reactant liquor, steam unreacted phosphoric acid (recycling), water entrainer toluene (recycling), obtain the mixture of viscous brown pentaerythritol phosphate and p-methyl benzenesulfonic acid.
Get 20g the said goods, 25g toluene, join and be equipped with in 500 mL four-hole bottles of thermometer, agitator, water knockout drum and spherical condensation tube, stir, heat to 60 DEG C after, drip 9.9g monoethanolamine with constant pressure funnel, and start timing, 30min dropwises, azeotropic 3h, separates aqueous phase refluxing toluene in water knockout drum.After reaction terminates.At more than vacuum 0.09MPa, decompression distillation is carried out to reactant liquor, steam water entrainer toluene (recycling), obtain faint yellow sticky shape target product, yield 76.2%.Be made into the 300g/L aqueous solution, arrange acrylic fabric, charcoal is long is 11.5cm, reaches national B1 grade standard.
embodiment three
Get 20g pentaerythrite, 72g phosphoric acid, 30g toluene joins and be equipped with in 500 mL four-hole bottles of thermometer, agitator, water knockout drum and spherical condensation tube, stir, be heated to 90 DEG C, add 7.4g NKC-9, and start timing, under the state of boiling, the water generate reaction and methylbenzene azeotropic steam, and separate aqueous phase refluxing toluene in water knockout drum.Reaction 5h, terminates reaction.Filter out catalyst n KC-9 while hot, at more than vacuum 0.09MPa, decompression distillation is carried out to filtrate, steams unreacted phosphoric acid (recycling), water entrainer toluene (recycling), obtain faint yellow thickness pentaerythritol phosphate.
After getting 24g the said goods, 6g water, 2g melamine, join in the 500 mL four-hole bottles that thermometer, agitator, spherical condensation tube are housed, stir, heating to 90 DEG C, start timing, reaction 0.5h.After reaction terminates, at more than vacuum 0.09MPa, decompression distillation is carried out to reactant liquor, steam dispersant water, obtain colourless transparent liquid, yield 95%.Be made into the 300g/L aqueous solution, arrange acrylic fabric, charcoal is long is 10.5cm, reaches national B1 grade standard.
Claims (16)
1. the acrylic fabric preparation method of multicomponent expansion type flame retardant, building-up process is divided into two steps, it is characterized in that:
Synthesis second step: add pentaerythritol phosphate, hydramine, water entrainer in the reactor, azeotropic reaction 3.5-5.5h, after having reacted, water entrainer is removed in decompression distillation, obtains brown viscous liquid product B; Or add pentaerythritol phosphate, a small amount of melamine, Shao Liangshui, 75-95 DEG C reaction in the reactor, reaction 0.5-2h, after having reacted, filter out unreacted melamine, decompression distillation is anhydrated, and obtains colourless viscous liquid product B; B is target product, multicomponent expansion type flame retardant.
2. the acrylic fabric preparation method of multicomponent expansion type flame retardant, building-up process is divided into two steps, it is characterized in that:
Synthesis second step: add pentaerythritol phosphate, water entrainer in the reactor, directly add or add hydramine in limited time in batches, the temperature that hydramine adds fashionable reaction system is 70-120 DEG C, azeotropic reaction 3.5-5.5h, after having reacted, water entrainer is removed in decompression distillation, obtains brown viscous liquid product B.
3. the acrylic fabric preparation method of multicomponent expansion type flame retardant described in claim 1,2, described amine substance is monoethanolamine, diethanol amine, triethanolamine.
4. the preparation method of multicomponent expansion type flame retardant of acrylic fabric described in claim 1, described amine substance is monoethanolamine, diethanol amine, triethanolamine, melamine.
5. the acrylic fabric preparation method of multicomponent expansion type flame retardant described in claim 1,2, described water entrainer is toluene etc.
6. the acrylic fabric preparation method of multicomponent expansion type flame retardant described in claim 1,2, described catalyst is sulfuric acid, p-methyl benzenesulfonic acid, cationic ion-exchange resin etc.
7. the acrylic fabric preparation method of multicomponent expansion type flame retardant described in claim 1,2, the azeotropic temperature that described hydramine and pentaerythritol phosphate react is between 120-140 DEG C.
8. the preparation method of multicomponent expansion type flame retardant of acrylic fabric described in claim 1, the reaction temperature of described melamine and pentaerythritol phosphate is between 75-95 DEG C.
9. the acrylic fabric preparation method of multicomponent expansion type flame retardant described in claim 1,2, the reaction time of described pentaerythritol phosphate and hydramine is between 3.5-5.5h.
10. the preparation method of multicomponent expansion type flame retardant of acrylic fabric described in claim 1, the reaction time of described pentaerythritol phosphate and melamine is between 0.5-2h.
The acrylic fabric preparation method of multicomponent expansion type flame retardant described in 11. claims 1,2, in the reaction of described pentaerythritol phosphate and hydramine, hydramine adds temperature between 70-120 DEG C.
The acrylic fabric preparation method of multicomponent expansion type flame retardant described in 12. claims 1,2, in the reaction of described pentaerythritol phosphate and hydramine, the joining day of hydramine is between 0-1h.
The acrylic fabric preparation method of multicomponent expansion type flame retardant described in 13. claims 1,2, described water entrainer amount is the 50-90% of material quality.
The acrylic fabric preparation method of multicomponent expansion type flame retardant described in 14. claims 1,2, the consumption of described NKC-9 is the 5-12% of material quality, and the catalytic amount such as the concentrated sulfuric acid, p-methyl benzenesulfonic acid is the 0.1-1% of material quality.
The acrylic fabric preparation method of multicomponent expansion type flame retardant described in 15. claims 1,2, the mass ratio of described pentaerythritol phosphate and hydramine is between 0.6-4.5.
The acrylic fabric preparation method of multicomponent expansion type flame retardant described in 16. claims 1, the mass ratio of described pentaerythritol phosphate and melamine is between 6-24.
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| CN201410569016.4A CN104389165A (en) | 2014-10-23 | 2014-10-23 | Preparation method for multi-component intumescent flame retardant for acrylic fabric |
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| CN201410569016.4A CN104389165A (en) | 2014-10-23 | 2014-10-23 | Preparation method for multi-component intumescent flame retardant for acrylic fabric |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109537278A (en) * | 2018-11-20 | 2019-03-29 | 吉林化工学院 | A kind of nitrogen phosphorus type flame-retardant agent and preparation method thereof |
| CN112480166A (en) * | 2020-11-30 | 2021-03-12 | 上海应用技术大学 | Preparation method of nitrogen-phosphorus flame retardant |
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| US3839506A (en) * | 1973-04-16 | 1974-10-01 | Borg Warner | Hindered phenol pentaerythritol phosphonate |
| CN1721423A (en) * | 2004-07-16 | 2006-01-18 | 中国石油天然气集团公司 | Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) |
| CN102633838A (en) * | 2012-04-08 | 2012-08-15 | 党庆风 | Synthesis and preparation method of double-hexa-phosphorus-ring diphosphonate flame retardant |
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2014
- 2014-10-23 CN CN201410569016.4A patent/CN104389165A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839506A (en) * | 1973-04-16 | 1974-10-01 | Borg Warner | Hindered phenol pentaerythritol phosphonate |
| CN1721423A (en) * | 2004-07-16 | 2006-01-18 | 中国石油天然气集团公司 | Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) |
| CN102633838A (en) * | 2012-04-08 | 2012-08-15 | 党庆风 | Synthesis and preparation method of double-hexa-phosphorus-ring diphosphonate flame retardant |
Non-Patent Citations (3)
| Title |
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| DENGHUI WU ET AL.: "Preparation and properties of flame retardant rigid polyurethane foam with phosphorus–nitrogen intumescent flame retardant", 《HIGH PERFORMANCE POLYMERS》 * |
| JINXUE JIANG ET AL.: "Effect of nitrogen phosphorus flame retardants on thermal degradation of wood", 《CONSTRUCTION AND BUILDING MATERIALS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109537278A (en) * | 2018-11-20 | 2019-03-29 | 吉林化工学院 | A kind of nitrogen phosphorus type flame-retardant agent and preparation method thereof |
| CN109537278B (en) * | 2018-11-20 | 2021-04-13 | 吉林化工学院 | Nitrogen-phosphorus flame retardant and preparation method thereof |
| CN112480166A (en) * | 2020-11-30 | 2021-03-12 | 上海应用技术大学 | Preparation method of nitrogen-phosphorus flame retardant |
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Application publication date: 20150304 |