CN105176061A - Preparation method of flame-retardant polyurethane resin - Google Patents
Preparation method of flame-retardant polyurethane resin Download PDFInfo
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- CN105176061A CN105176061A CN201510713988.0A CN201510713988A CN105176061A CN 105176061 A CN105176061 A CN 105176061A CN 201510713988 A CN201510713988 A CN 201510713988A CN 105176061 A CN105176061 A CN 105176061A
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- cyclodextrin
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Abstract
The invention relates to a preparation method of flame-retardant polyurethane resin. The preparation method comprises the steps of adding cyclodextrin and resorcinol bi(diphenyl) phosphate (RDP) to a solvent, conducting mixing, and obtaining a cyclodextrin/RDP compound; making the cyclodextrin/RDP compound be subjected to still standing for seimentation, filteration, vacuum drying and washing, and obtaining a cyclodextrin/RDP clathrate compound; adding the cyclodextrin/RDP clathrate compound to polyuretane resin, then adding the solvent, stirring the mixture uniformly, leaving the mixture still standing, conducting defoaming and formation, and obtaining the flame-retardant polyurethane resin. The preparation method of the flame-retardant polyurethane resin is simple and easy to control, the problems that resorcinol diphenyl phosphate is poor in dispersity in a base body and prone to migrating when serving as fire retardant can be solved, and meanwhile the mechanical property and the flame retardant property of polyurethane are substantially improved.
Description
Technical field
The invention belongs to the preparation field of flame-retarded resin material, particularly a kind of preparation method of flame retardant polyurethane resin.
Background technology
The advantages such as urethane foam has that thermal conductivity is low, cohesive force is strong, good waterproof performance are the best building thermal insulation materials of current performance.2014, wall heat insulation material urethane was pushed to public's " bench " by " big fire of Jing'an Monastery, Shanghai " accident, the application of the not good serious restriction urethane of polyurethane flame-proof.Urethane flame-retardant modified in the industrial production mainly through physics addition manner, the method has certain defect: the bad dispersibility of fire retardant in urethane, easily produces reunion, causes material over-all properties to decline; On the other hand, after of long duration, easily there is migration and cause flame retardant effect to be deteriorated in fire retardant.For above problem, need to develop a kind of novel flame-retardant additive, improve product performance.
Cyclodextrin is the cyclic oligomer sugar compounds linked with α-Isosorbide-5-Nitrae glucoside key by 6 to 12 glucopyranose units.Cyclodextrin molecular becomes cone post shapes, and cavity inside arranges joins glycosyloxy atom, and Glucopyranose ring hydrogen atom is positioned at cavity and covers and join glycosyloxy atom, makes cavity inside become hydrophobicity space; Molecule outer ledge assembles a lot of hydroxyl, and have very strong wetting ability, cyclodextrin molecular can the many guest molecules of inclusion by means of the special cavity structure of its " interior hydrophobic, outer hydrophilic ".(Wang Chaoxia, Liu Liya, remaining water woods. beta-cyclodextrin prepares mechanism and the application [J] thereof of essence microcapsule. dyeing and printing auxiliary, 2003,04:5-7.) the easy crystallization of beta-cyclodextrin, separation, purification, nontoxic, readily biodegradable, has been widely used in the every field such as chemical industry, medicine, food, dyestuff.And cyclodextrin inclusion compound has no report for polyurethane flame-proof aspect.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of flame retardant polyurethane resin, and obtained flame-retardant polyurethane resin material of the present invention has good mechanical property and flame retardant effect.
The preparation method of a kind of flame retardant polyurethane resin of the present invention, comprising:
(1) join in solvent by cyclodextrin and two (phenylbenzene) the phosphoric acid ester RDP of Resorcinol, mixing, obtains cyclodextrin/RDP mixture;
(2) above-mentioned cyclodextrin/RDP mixture carry out staticly settling, filter, vacuum-drying, washing, obtains cyclodextrin/RDP inclusion compound;
(3) above-mentioned cyclodextrin/RDP inclusion compound is added in urethane resin, then adds solvent, stir, leave standstill, deaeration, shaping, obtain flame retardant polyurethane resin.
Described step (1) cyclodextrin is beta-cyclodextrin.
The mol ratio of described step (1) cyclodextrin and RDP is 1:0-1:8; The mass ratio of cyclodextrin and solvent is 1:5-1:15.
In described step (1), mixing condition is: under 50-70 DEG C of condition, mechanical stirring 1-3h.
In described step (2), washing is washed for adding ethanol.
Add ethanol to carry out washing and be: the concentration of ethanol is 98%, and the mass ratio of cyclodextrin/RDP mixture and ethanol is that 1:5-1:10 washs.
The solvent of described step (1), (3) is N,N-DIMETHYLACETAMIDE (DMAc).
In described step (3), the mass percentage of flame retardant polyurethane resin cyclodextrin/RDP inclusion compound is 5-30%.
In described step (3), the solid content of flame retardant polyurethane resin is 20-25%.
beneficial effect
The inventive method is simple and easy to control, can overcome two (phenylbenzene) phosphoric acid ester of Resorcinol as the fire retardant problem such as bad dispersibility, easy migration in the base, increase substantially mechanical property and the flame retardant properties of urethane simultaneously;
The fire-retardant rank of cyclodextrin inclusion compound modified polyurethane material prepared by the present invention can reach UL94V-1 rank, belongs to higher fire-retardant rank;
Cyclodextrin inclusion compound modified polyurethane resin prepared by the present invention has more excellent mechanical property.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) 3.08g beta-cyclodextrin and two (phenylbenzene) phosphoric acid ester of 1.54g Resorcinol are joined in the DMAc solution of 30ml, under 50 DEG C of conditions, fully mix 1h, form beta-cyclodextrin/RDP mixture;
(2) staticly settle, filter, vacuum-drying, add 10ml ethanol, wash unnecessary RDP, obtain beta-cyclodextrin/RDP inclusion compound;
(3) get 0.53g beta-cyclodextrin/RDP inclusion compound, adding to 35g solid content is in 30% urethane resin, adds 16mlDMAc and dissolves, stir under room temperature, leave standstill, deaeration, shaping, prepares polyurethane flame-proof film and batten.
Embodiment 2
(1) 3.27g beta-cyclodextrin and two (phenylbenzene) phosphoric acid ester of 3.27g Resorcinol are joined in the DMAc solution of 30ml, under 55 DEG C of conditions, fully mix 2h, form beta-cyclodextrin/RDP mixture;
(2) staticly settle, filter, vacuum-drying, add 15ml ethanol, wash unnecessary RDP, obtain beta-cyclodextrin/RDP inclusion compound;
(3) get 1.05g beta-cyclodextrin/RDP inclusion compound, adding to 35g solid content is in 30% urethane resin, adds 14mlDMAc and dissolves, stir under room temperature, leave standstill, deaeration, shaping, prepares polyurethane flame-proof film and batten.
Embodiment 3
(1) 2.59g beta-cyclodextrin and two (phenylbenzene) phosphoric acid ester of 5.18g Resorcinol are joined in the DMAc solution of 25ml, under 60 DEG C of conditions, fully mix 3h, form beta-cyclodextrin/RDP mixture;
(2) staticly settle, filter, vacuum-drying, add 25ml ethanol, wash unnecessary RDP, obtain beta-cyclodextrin/RDP inclusion compound;
(3) get 1.58g beta-cyclodextrin/RDP inclusion compound, adding to 35g solid content is in 30% urethane resin, adds 12mlDMAc and dissolves, stir under room temperature, leave standstill, deaeration, shaping, prepares polyurethane flame-proof film and batten.
Embodiment 4
(1) 3.67g beta-cyclodextrin and two (phenylbenzene) phosphoric acid ester of 10.23g Resorcinol are joined in the DMAc solution of 35ml, under 65 DEG C of conditions, fully mix 2h, form beta-cyclodextrin/RDP mixture;
(2) staticly settle, filter, vacuum-drying, add 50ml ethanol, wash unnecessary RDP, obtain beta-cyclodextrin/RDP inclusion compound;
(3) get 2.10g beta-cyclodextrin/RDP inclusion compound, adding to 35g solid content is in 30% urethane resin, adds 10mlDMAc and dissolves, stir under room temperature, leave standstill, deaeration, shaping, prepares polyurethane flame-proof film and batten.
Embodiment 5
(1) 4.90g beta-cyclodextrin and two (phenylbenzene) phosphoric acid ester of 18.97g Resorcinol are joined in the DMAc solution of 50ml, under 65 DEG C of conditions, fully mix 3h, form beta-cyclodextrin/RDP mixture;
(2) staticly settle, filter, vacuum-drying, add 90ml ethanol, wash unnecessary RDP, obtain beta-cyclodextrin/RDP inclusion compound;
(3) get 2.63g beta-cyclodextrin/RDP inclusion compound, adding to 35g solid content is in 30% urethane resin, adds 8mlDMAc and dissolves, stir under room temperature, leave standstill, deaeration, shaping, prepares polyurethane flame-proof film and batten.
Embodiment 6
(1) 6.30g beta-cyclodextrin and two (phenylbenzene) phosphoric acid ester of 22.60g Resorcinol are joined in the DMAc solution of 60ml, under 70 DEG C of conditions, fully mix 2h, form beta-cyclodextrin/RDP mixture;
(2) staticly settle, filter, vacuum-drying, add 100ml ethanol, wash unnecessary RDP, obtain beta-cyclodextrin/RDP inclusion compound;
(3) get 3.15g beta-cyclodextrin/RDP inclusion compound, adding to 35g solid content is in 30% urethane resin, adds 6mlDMAc and dissolves, stir under room temperature, leave standstill, deaeration, shaping, prepares polyurethane flame-proof film and batten.
Comparative example
Get 0.53g beta-cyclodextrin/RDP inclusion compound, adding to 35g solid content is in 30% urethane resin, adds 16mlDMAc and dissolves, stir under room temperature, leave standstill, deaeration, shaping, prepares polyurethane flame-proof film and batten.
By the concrete enforcement to embodiment and comparative example above, the mechanical property of different embodiment and comparative example is as following table:
Fire retardant material the present invention obtained, according to UL94 standard, gets 5 sample tests to each embodiment.
Samples vertical placed, regulate sample position, 6mm is clamped by sample holder in upper end, the medical absorbent cotton layer 300mm that lower end is laid apart from level.Be that the Bunsen burner of (20 soil 2) mm applies flame 10 seconds at 10mm place, sample lower surface with flame height, remove flame, timing, observe phenomena.
Through test, the result of embodiment and comparative example is as follows:
| Physicals | A | B | C | D | E | F |
| Comparative example | 95 | 475 | -- | Be | Be | HB |
| Embodiment 1 | 120 | 600 | -- | Be | Be | HB |
| Embodiment 2 | 22 | 340 | 46 | No | Be | V-2 |
| Embodiment 3 | 17 | 250 | 33 | No | No | V-1 |
| Embodiment 4 | 15 | 225 | 30 | No | No | V-1 |
| Embodiment 5 | 12 | 175 | 23 | No | No | V-1 |
| Embodiment 6 | 8 | 125 | 17 | No | No | V-1 |
A: average each sample apply at every turn flame from flaming combustion after fire time/s
B: often organize 5 samples apply 10 flame from flaming combustion after fire summation time/s
C: average each sample second time apply flame after fire aphlogistic time/s
D: whether each sample flaming combustion or flameless combustion spread to fixture
E: whether each sample dropping ignites the phenomenon of medical absorbent cotton
F:UL94 standard.
Claims (9)
1. a preparation method for flame retardant polyurethane resin, comprising:
(1) join in solvent by cyclodextrin and two (phenylbenzene) the phosphoric acid ester RDP of Resorcinol, mixing, obtains cyclodextrin/RDP mixture;
(2) above-mentioned cyclodextrin/RDP mixture carry out staticly settling, filter, vacuum-drying, washing, obtains cyclodextrin/RDP inclusion compound;
(3) above-mentioned cyclodextrin/RDP inclusion compound is added in urethane resin, then adds solvent, stir, leave standstill, deaeration, shaping, obtain flame retardant polyurethane resin.
2. the preparation method of a kind of flame retardant polyurethane resin according to claim 1, is characterized in that: described step (1) cyclodextrin is beta-cyclodextrin.
3. the preparation method of a kind of flame retardant polyurethane resin according to claim 1, is characterized in that: the mol ratio of described step (1) cyclodextrin and RDP is 1:0-1:8; The mass ratio of cyclodextrin and solvent is 1:5-1:15.
4. the preparation method of a kind of flame retardant polyurethane resin according to claim 1, is characterized in that: in described step (1), mixing condition is: under 50-70 DEG C of condition, mechanical stirring 1-3h.
5. the preparation method of a kind of flame retardant polyurethane resin according to claim 1, is characterized in that: in described step (2), washing is washed for adding ethanol.
6. the preparation method of a kind of flame retardant polyurethane resin according to claim 5, is characterized in that: add ethanol and carry out washing and be: the concentration of ethanol is 98%, and the mass ratio of cyclodextrin/RDP mixture and ethanol is that 1:5-1:10 washs.
7. the preparation method of a kind of flame retardant polyurethane resin according to claim 1, is characterized in that: the solvent of described step (1), (3) is N,N-DIMETHYLACETAMIDE DMAc.
8. the preparation method of a kind of flame retardant polyurethane resin according to claim 1, is characterized in that: in step (3), the mass percentage of flame retardant polyurethane resin cyclodextrin/RDP inclusion compound is 5-30%.
9. the preparation method of a kind of flame retardant polyurethane resin according to claim 1, is characterized in that: in step (3), the solid content of flame retardant polyurethane resin is 20-25%.
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Cited By (3)
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| CN107383638A (en) * | 2017-08-24 | 2017-11-24 | 江苏浦漕科技股份有限公司 | A kind of high fire-retardance high-temperature resistant cable insulation material and preparation method |
| CN109134802A (en) * | 2017-06-27 | 2019-01-04 | 万华化学集团股份有限公司 | A kind of phosphor-containing halogen-free flame retardant thermoplastic polyurethane elastomer composition and its preparation method and application |
| CN115651207A (en) * | 2022-10-14 | 2023-01-31 | 江西省安安科技有限公司 | In-situ polymerization flame retardant and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109134802A (en) * | 2017-06-27 | 2019-01-04 | 万华化学集团股份有限公司 | A kind of phosphor-containing halogen-free flame retardant thermoplastic polyurethane elastomer composition and its preparation method and application |
| CN109134802B (en) * | 2017-06-27 | 2023-09-19 | 万华化学集团股份有限公司 | Phosphorus-containing halogen-free flame-retardant thermoplastic polyurethane elastomer composition and preparation method and application thereof |
| CN107383638A (en) * | 2017-08-24 | 2017-11-24 | 江苏浦漕科技股份有限公司 | A kind of high fire-retardance high-temperature resistant cable insulation material and preparation method |
| CN115651207A (en) * | 2022-10-14 | 2023-01-31 | 江西省安安科技有限公司 | In-situ polymerization flame retardant and preparation method thereof |
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Application publication date: 20151223 |