CN103360606B - Halogen-free organophosphate fire retardant and its preparation method - Google Patents
Halogen-free organophosphate fire retardant and its preparation method Download PDFInfo
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Abstract
The invention relates to a halogen-free organophosphate fire retardant and its preparation method. The fire retardant contains no halogen and will not release corrosive toxic gases when combusted. Through a reaction between polycarbonate polyol and isocyanate, an inflaming retarding element is embedded into a polyurethane foamed material and will not migrate or escape when the material is heated. Thus, the material is permanently endowed with flame resistance.
Description
Technical field
The present invention relates to a kind of halogen-free organophosphorous ester flame-proof agent and preparation method thereof, belong to resistance combustion polyurethane foam field.
Background technology
Polyurethane foam is widely used in building thermal insulation material, furniture, seat cushions etc.Because it is inflammable, the flame-retardant modified focus having become this area research is carried out to polyurethane foam.Most widely used is at present halogenated flame retardant, but there is easily migration, loss, flame retardant resistance can not be lasting, and produce the defect such as more smog and poisonous gas (hydrogen halide) during burning, therefore halogenated flame retardant does not meet increasingly strict non-halogen requirement.By comparison, reactive phosphorus flame retardant has that consumption is low, flame retardant resistance lasting stability and burning time do not discharge the features such as corrosive gases, be the flame-retardant modified better selection of polyurethane foam.
Chinese patent 201010227072.1 discloses a kind of preparation method of oligomerization phosphate polyalcohol, use the straight or branched monohydroxy-alcohol and phosphorus oxychloride synthesis dichloro oxygen phosphorus list alkane ester with 1 ~ 4 carbon atom, then aggregate into oligomerization phosphate polyalcohol with dibasic alcohol.Because product water dissolubility is large, need, with the larger acid binding agent triethylamine of toxicity and methylene dichloride removing byproduct hydrogen chloride, toxic substance be caused to remain.
Summary of the invention
The object of this invention is to provide the halogen-free organophosphorous ester flame-proof agent of a kind of response type, this fire retardant overcomes the deficiency in above-mentioned phosphoric acid ester performance, and solves the problem introducing toxic residua except byproduct hydrogen chloride.
Another object of the present invention is to provide a kind of method preparing halogen-free organophosphorous ester flame-proof agent, and the application of this fire retardant in polyurethane foam.
For achieving the above object, the present invention adopts following technical scheme:
Described halogen-free organophosphorous ester flame-proof agent, its structural formula is as follows:
Wherein, R represents octyl group, iso-octyl, benzyl, phenyl ring; Polymerization degree n is the positive integer of 1 ~ 10.
In the structural formula of described halogen-free organophosphorous ester flame-proof agent, polymerization degree n preferably 4 ~ 10 positive integer.
The preparation method of described halogen-free organophosphorous ester flame-proof agent is as follows:
(1) monohydroxy-alcohol (phenol) and phosphorus oxychloride according to 1: 1 mol ratio, first phosphorus oxychloride is placed in reactor, monohydroxy-alcohol (phenol) is slowly dripped under stirring, time for adding is 1 ~ 3 hour, wait to dropwise, slowly heat up, keep temperature 30 ~ 80 DEG C reaction 1 ~ 2 hour, the hydrogenchloride of generation is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
(2) dibasic alcohol and phosphorus oxychloride according to 1.1 ~ 2: 1 mol ratio, again dibasic alcohol is slowly instilled in reactor, time for adding is 0.25 ~ 0.75 hour, be warming up to 80 ~ 90 DEG C after dropwising and continue stirring 1 ~ 3 hour, the hydrogenchloride of generation is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases simultaneously;
(3) gained reaction solution is transferred to extraction kettle, control temperature 20 ~ 30 DEG C, repeatedly washing until aqueous phase to drip silver nitrate solution not muddy, then add 1% ~ 5% anhydrous sodium sulphate and carry out drying, filtration, obtain described hydroxyl fire retardant of polyphosphate.
The method of the halogen-free organophosphorous ester flame-proof agent of described preparation, is characterized in that, monohydroxy-alcohol (phenol) described in step (1) is phenol, any one in phenylcarbinol, octanol, isooctyl alcohol.
The method of the halogen-free organophosphorous ester flame-proof agent of described preparation, is characterized in that, monohydroxy-alcohol (phenol) described in step (1) is phenylcarbinol or phenol.
The method of the halogen-free organophosphorous ester flame-proof agent of described preparation, is characterized in that, dibasic alcohol described in step (2) is any one in ethylene glycol, 1,2-PD, BDO.
The described application of halogen-free organophosphorous ester flame-proof agent in polyurethane hard foam, polyurethane foams.
Technical scheme of the present invention is described in further detail as follows:
The molecular structure of described halogen-free organophosphorous ester flame-proof agent is as follows:
Wherein, R is octyl group, iso-octyl, benzyl, phenyl ring;
Polymerization degree n is the positive integer of 1 ~ 10, preferably the positive integer of 4 ~ 10.
The preparation method of described halogen-free organophosphorous ester flame-proof agent is as follows:
(1) phosphorus oxychloride is placed in reactor, slowly drips monohydroxy-alcohol (phenol) under stirring, wait to dropwise, slow intensification, keeps temperature 30 ~ 80 DEG C reaction 1 ~ 2 hour, the hydrogenchloride of generation is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases, wherein, temperature of reaction preferably controls, at 40 ~ 50 DEG C, to be more preferably 45 ~ 50 DEG C, time for adding is 1 ~ 3 hour, be preferably 1 ~ 2 hour, obtain reaction solution, reaction formula is:
(2) dibasic alcohol is slowly instilled in reaction solution, be warming up to 80 ~ 90 DEG C after dropwising and continue stirring 1 ~ 3 hour, preferably 2 hours, the hydrogenchloride of generation is introduced the absorption unit that water is housed simultaneously, until concentration of hydrochloric acid no longer increases, wherein, temperature of reaction preferably controls at 85 ~ 90 DEG C, more preferably 90 DEG C, time for adding is 0.25 ~ 0.75 hour, be preferably 0.5 hour, obtain mixture, reaction equation is:
(3) gained reaction solution is transferred to extraction kettle, control temperature 20 ~ 30 DEG C, preferably 30 DEG C, washing is until aqueous phase dropping silver nitrate solution is not muddy repeatedly, then represent that in product, chlorion eliminates substantially, add 1% ~ 5% anhydrous sodium sulphate again and carry out drying, filtration, obtain described hydroxyl fire retardant of polyphosphate.
Described monohydroxy-alcohol (phenol) is octanol, any one in isooctyl alcohol, phenylcarbinol, phenol, and preferred phenylcarbinol, phenol, be more preferably phenol, and monohydroxy-alcohol (phenol) is 1: 1 with the mol ratio of phosphorus oxychloride.
Described dibasic alcohol is any one in ethylene glycol, 1,2-PD, BDO, and the mol ratio of dibasic alcohol and phosphorus oxychloride is 1.1 ~ 2: 1, preferably 1.1 ~ 1.5: 1, more preferably 1.1: 1.
Contriver is found by great many of experiments, when monohydroxy-alcohol (phenol) being elected as octanol, isooctyl alcohol, phenylcarbinol, phenol (namely R base is octyl group, iso-octyl, benzyl, phenyl ring), the hydrophobicity of poly phosphate of the present invention is comparatively strong, and washing can remove byproduct hydrogen chloride.When preparing polyurethane flexible foam and rigid foam with poly phosphate of the present invention, the flame retardant properties of this polyurethane foam meets national standard after testing.In addition, exceed contriver it is contemplated that the introducing of hydrophobic side chains (i.e. R side chain) significantly improves the uniformity coefficient of polyurethane foam, during foaming, do not add the foam that foam stabilizer also can obtain uniform foam cell densification.R side chain is on the hydrophobicity of poly phosphate and test as follows on the impact of polyurethane foam uniformity coefficient:
According to the preparation method of embodiment 1, only change the kind of monohydroxy-alcohol (phenol) in step (1), namely phenylcarbinol, octanol, isooctyl alcohol, propyl carbinol, methyl alcohol, ethanol, n-propyl alcohol, the isopropylcarbinol of 1 mole is added respectively, the poly phosphate sample 1,2,3,4,5,6,7,8 of obtained different R side chain.The method removing byproduct hydrogen chloride washed with water again, finally by above-mentioned sample through the obtained polyurethane foam that foams (foaming formulation and reaction conditions constant), observe the uniformity coefficient of foam, detected result is as shown in the table:
Table 1---R side chain is on poly phosphate hydrophobicity and the impact on foam uniformity coefficient
| Monohydroxy-alcohol (phenol) | Phase-splitting degree * | Foamy appearance | |
| Embodiment 1 | Phenol | ++ | Foam is even, fine and close |
| Sample 1 | Phenylcarbinol | ++ | Foam is even, fine and close |
| Sample 2 | Octanol | + | Foam is even, fine and close |
| Sample 3 | Isooctyl alcohol | + | Foam is even, fine and close |
| Sample 4 | Propyl carbinol | + | Foam is uneven |
| Sample 5 | Methyl alcohol | - | \ |
| Sample 6 | Ethanol | - | \ |
| Sample 7 | N-propyl alcohol | - | \ |
| Sample 8 | Isopropylcarbinol | - | \ |
Remarks: phase-splitting degree represents very easily phase-splitting for " ++ ", and poly phosphate and water are completely incompatible; "+" represents can phase-splitting, have part poly phosphate and water miscible; "-" represents can not phase-splitting, and poly phosphate is water-soluble.Poly phosphate, after washing, if phase-splitting, then represents that the hydrophobicity of this poly phosphate is good, and washing is not until to drip silver nitrate solution in aqueous phase muddy repeatedly, represents that in product, chlorion eliminates substantially; If can not phase-splitting, then represent that this poly phosphate is greatly water-soluble, washing cannot remove byproduct hydrogen chloride.
Result display in table, when the R side chain substituents of poly phosphate is phenyl ring, benzyl, octyl group, iso-octyl, its hydrophobicity is obviously better than the alkyl poly phosphate that side chain is 1 ~ 4 carbon atom, can remove byproduct hydrogen chloride, and significantly improve the uniformity coefficient of polyurethane foam by washing.
Compared with prior art, feature of the present invention is:
1., in the process of preparation poly phosphate of the present invention, washing can remove byproduct hydrogen chloride, simplifies aftertreatment technology,
Not only environmental protection but also reduce costs;
2. the uniformity coefficient of polyurethane foam is improved, without the need to adding foam stabilizer;
3. flame retarding efficiency high and do not move, not loss, make material have lasting flame retardant properties;
4. not halogen-containing, burning time do not discharge corrodibility toxic gas.
Embodiment
With specific embodiment, the present invention will be further described below, but should not be construed as limiting the scope of the invention.
Embodiment 1: the preparation of organophosphate of the present invention
1. 153.5 grams of (1 mole) phosphorus oxychloride are added in reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip 94 grams of phenol (1 mole) of melting in advance again, total time for adding about 1 hour, 70 ~ 80 DEG C of reactions 2 hours after dropwising, the hydrogenchloride of generation is introduced the absorption unit that water is housed by period, until concentration of hydrochloric acid no longer increases;
2. 68.2 grams of ethylene glycol (1.1 moles) are slowly added in still, time for adding is 0.25 hour, control temperature of charge between 80 ~ 90 DEG C, continue reaction 2 hours, the hydrogenchloride of generation is introduced the absorption unit that water is housed by period, until concentration of hydrochloric acid no longer increases;
3. gained reaction solution is transferred to separating funnel, control temperature 30 DEG C, washing is until aqueous phase is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, adding 3% anhydrous sodium sulphate again carries out being dried to limpid, obtain light yellow transparent liquid after filtration, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is about 15%, and hydroxyl value is 51mgKOH/g, and the viscosity at 25 DEG C is 1080mPaS, and acid number is 0.5mgKOH/g.
Embodiment 2: the preparation of organophosphate of the present invention
1. 153.5 grams of (1 mole) phosphorus oxychloride are added in reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip 108.1 grams of phenylcarbinols (1 mole), total time for adding is 2 hours, 30 ~ 40 DEG C of reactions 1 hour after dropwising, the hydrogenchloride of generation is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
2. 68.2 grams of ethylene glycol (1.1 moles) are slowly added in still, time for adding is 0.5 hour, control temperature of charge between 80 ~ 90 DEG C, continue reaction 2 hours, the hydrogenchloride of generation is introduced the absorption unit that water is housed by period, until concentration of hydrochloric acid no longer increases;
3. gained reaction solution is transferred to extraction kettle, control temperature 30 DEG C, washing is until aqueous phase is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, then adds 1% anhydrous sodium sulfate drying to limpid, obtain light yellow transparent liquid after filtration, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is 14%, and hydroxyl value is 51mgKOH/g, and the viscosity at 25 DEG C is 950mPaS, and acid number is 0.4mgKOH/g.
Embodiment 3: the preparation of organophosphate of the present invention
1. first 153.5 grams of (1 mole) phosphorus oxychloride are added in reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip 130.2 grams of octanols (1 mole), total time for adding is 3 hours, 30 ~ 40 DEG C of reactions 1.5 hours after dropwising, the hydrogenchloride of generation is introduced the absorption unit that water is housed by period, until concentration of hydrochloric acid no longer increases;
2. then by 152.2 gram 1,2-propylene glycol (2 moles) slowly adds in still, and time for adding is 0.75 hour, controls temperature of charge between 80 ~ 90 DEG C, continues reaction 1 hour, the hydrogenchloride of generation is introduced the absorption unit that water is housed by period, until concentration of hydrochloric acid no longer increases;
3. again gained reaction solution is transferred to separating funnel, control temperature 20 DEG C, washing is until aqueous phase is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, add 3% anhydrous sodium sulfate drying again to limpid, obtain light yellow transparent liquid after filtration, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is 10%, and hydroxyl value is 340mgKOH/g, and the viscosity at 25 DEG C is 700mPaS, and acid number is 0.5mgKOH/g.
Embodiment 4: the preparation of organophosphate of the present invention
1. first 153.5 grams of (1 mole) phosphorus oxychloride are added in reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip 130.2 grams of isooctyl alcohol (1 mole), total time for adding is 3 hours, 30 ~ 40 DEG C of reactions 1.5 hours after dropwising, the hydrogenchloride of generation is introduced the absorption unit that water is housed by period, until concentration of hydrochloric acid no longer increases;
2. then by 135 gram 1,4-butyleneglycol (1.5 moles) slowly adds in still, and time for adding is 0.5 hour, controls temperature of charge between 80 ~ 90 DEG C, continues reaction 3 hours, the hydrogenchloride of generation is introduced the absorption unit that water is housed by period, until concentration of hydrochloric acid no longer increases;
3. again gained reaction solution is transferred to separating funnel, control temperature 25 DEG C, washing is until aqueous phase is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, adding 5% anhydrous sodium sulphate again carries out being dried to limpid, obtain light yellow transparent liquid after filtration, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is 10%, and hydroxyl value is 370mgKOH/g, and the viscosity at 25 DEG C is 800mPaS, and acid number is 0.2mgKOH/g.
Embodiment 5: the halogen-free organophosphorous acid esters of the present invention is in the application of polyurethane flexible foam
(molecular mass is 3000g/mol to get the made hydroxyl poly phosphate of 15 grams of embodiments 1 to 4 and 100 grams of polyether glycols respectively, trifunctional, hydroxyl value is 56mgKOH/g) mixing, solidifying agent is made with TDI (tolylene diisocyanate), and add 0.4 gram of N, N-dimethylethanolamine, 0.2 gram of stannous octoate carries out foaming experiment, tests the performance of soft foam materials after slaking.Foaming envrionment temperature is 20 ± 1 DEG C, and temperature of charge is 20 ± 0.5 DEG C, stirring velocity 2500 revs/min, churning time 5 ~ 10 seconds.According to the flame retardant properties of the made soft foam of standard test of GB8410-2006 (i.e. " combustioncharacteristics of automotive interior material "), result is as shown in table 2:
Table 2 hydroxyl poly phosphate is in the application (according to GB8410-2006) of polyurethane foams
Embodiment 6: the halogen-free organophosphorous acid esters of the present invention is in the application of hard polyurethane foam
(molecular mass is 3000g/mol to get the made hydroxyl poly phosphate of 30 grams of embodiments 1 to 4 and 100 grams of polyether glycols respectively, trifunctional, hydroxyl value is 56mgKOH/g) mixing, solidifying agent is made with thick MDI (diphenylmethanediisocyanate), add 1.8g dimethyl cyclohexane again, 1.2 grams of DMP-30,25 grams of whipping agents (141b) carry out foaming experiment, test the performance of stiff foam material after slaking.Foaming envrionment temperature is 20 ± 1 DEG C, and temperature of charge is 20 ± 0.5 DEG C, stirring velocity 2500 revs/min, churning time 5-10 second.According to the flame retardant properties of the made rigid foam of standard test of GB8624-2006 (i.e. " material of construction and product burns grading performance "), result is as shown in table 3:
Table 3 hydroxyl poly phosphate is in the application (according to GB8624-2006) of polyurethane hard foam
The test result of embodiment 5 and embodiment 6 shows: after adding fire retardant of the present invention, and the flame retardant properties of urethane plastic significantly improves, and all reaches excellent fire-retardant index.
Claims (7)
1. a halogen-free organophosphorous ester flame-proof agent, structural formula is as follows:
Wherein, R represents octyl group, iso-octyl, benzyl, phenyl ring; Polymerization degree n is the positive integer between 1 ~ 10.
2. halogen-free organophosphorous ester flame-proof agent according to claim 1, is characterized in that, polymerization degree n is the positive integer between 4 ~ 10.
3. halogen-free organophosphorous ester flame-proof agent according to claim 1, is characterized in that, the preparation method of described halogen-free organophosphorous ester flame-proof agent, comprises the steps:
(1) monohydroxy-alcohol or monohydric phenol and phosphorus oxychloride according to 1: 1 mol ratio, first phosphorus oxychloride is placed in reactor, stir lower slowly dropping monohydroxy-alcohol or monohydric phenol, time for adding is 1 ~ 3 hour, wait to dropwise, slowly heat up, keep temperature 30 ~ 80 DEG C reaction 1 ~ 2 hour, the hydrogenchloride of generation is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
(2) dibasic alcohol and phosphorus oxychloride according to 1.1 ~ 2: 1 mol ratio, again dibasic alcohol is slowly instilled in reactor, time for adding is 0.25 ~ 0.75 hour, be warming up to 80 ~ 90 DEG C after dropwising and continue stirring 1 ~ 3 hour, the hydrogenchloride of generation is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases simultaneously;
(3) gained reaction solution is transferred to extraction kettle, control temperature 20 ~ 30 DEG C, repeatedly washing until aqueous phase to drip silver nitrate solution not muddy, then add 1% ~ 5% anhydrous sodium sulphate and carry out drying, filtration, obtain described hydroxyl fire retardant of polyphosphate.
4. halogen-free organophosphorous ester flame-proof agent according to claim 3, is characterized in that, in described step (1), monohydroxy-alcohol or monohydric phenol are any one in phenol, phenylcarbinol, octanol, isooctyl alcohol.
5. halogen-free organophosphorous ester flame-proof agent according to claim 3, is characterized in that, in described step (1), monohydroxy-alcohol or monohydric phenol are phenylcarbinol or phenol.
6. halogen-free organophosphorous ester flame-proof agent according to claim 3, is characterized in that, in described step (2), dibasic alcohol is any one in ethylene glycol, 1,2-PD, BDO.
7. the application of halogen-free organophosphorous ester flame-proof agent in hard polyurethane foam, polyurethane flexible foam described in any one of claim 1 ~ 6.
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| CN108383973B (en) * | 2018-02-12 | 2020-12-22 | 吴艳飞 | Full-water foaming spraying soft flame-retardant polyurethane thermal insulation material and preparation method thereof |
| CN115873257B (en) * | 2021-09-29 | 2024-04-09 | 中国石油化工股份有限公司 | Halogenated polyphosphate polyol and polyurea elastomer, and preparation methods and applications thereof |
| CN115353605A (en) * | 2022-09-15 | 2022-11-18 | 恩龙实业(嘉兴)有限公司 | In-situ flame-retardant polyurethane foam material and preparation method thereof |
| CN116333286B (en) * | 2023-05-08 | 2024-07-02 | 广州光通科技有限公司 | Flame retardant with high phosphorus content and preparation method thereof |
| CN116694211A (en) * | 2023-05-31 | 2023-09-05 | 广州也乐新材料科技有限公司 | Preparation method and application of water-based two-component polyurethane flame-retardant material |
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