CN105860505A - Preparation method of high-flame-retardancy modified polyurethane composite material - Google Patents
Preparation method of high-flame-retardancy modified polyurethane composite material Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C08L75/08—Polyurethanes from polyethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
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- C08G18/381—Polyhydroxy compounds having chlorine and/or bromine atoms having bromine atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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Abstract
The invention discloses a preparation method of a high-flame-retardancy modified polyurethane composite material. The method comprises the following steps: adding gamma-aminoethyl amino propyl trimethoxy silane, N,N-dimethyl cyolohexlemine and tetrahydrofuran into a reaction container, and adding phenyl dichlorophosphate for reacting to obtain a P-N-Si flame retardant; uniformly mixing expandable graphite, zinc stannate, the P-N-Si flame retardant, attapulgite, montmorillonite, hollow glass microspheres, nanometer titanium dioxide, expanded vermiculite, graphene, pentaerythritol and anilmomethyl triethoxy silane to obtain a composite material; stirring polyether polyol, the composite material, diphenyl methane diisocyanate, stannous octoate, trimethylolpropane and dibromoneopentyl glycol, adding epoxy resin, acrylic resin, dimethythiotoluene diamine and 4,4'-methylene-bis-o-toluidine, stirring and curing. The preparation method of the high-flame-retardancy modified polyurethane composite material disclosed by the invention is simple in steps, and the obtained material has high intensity and high flame retardancy.
Description
Technical field
The present invention relates to polyurethanes technology field, particularly relate to a kind of high fire-retardance modified polyurethane composite
Preparation method.
Background technology
Polyurethane is the general designation on main chain containing the macromolecular compound repeating carbamate groups, has excellent
The characteristics such as different wear-resisting, oil resistant, tear-resistant, resistance to chemical attack, its purposes is very wide, can substitute for rubber,
Plastics, nylon etc., for airport, hotel, building materials, automobile factory, colliery factory, cement plant, condo,
The fields such as villa, landscaping, colored stone art, park.But common polyurethane material easily burns,
There is during application the biggest fire safety evaluating hidden danger, greatly limit polyurethane material in practice should
With.
Summary of the invention
The technical problem existed based on background technology, the present invention proposes a kind of high fire-retardance modified polyurethane and is combined
The preparation method of material, its step is simple, mild condition, and the composite material strength obtained is high, fire resistance
Excellence, can meet the use requirement of multiple fields.
The preparation method of a kind of high fire-retardance modified polyurethane composite that the present invention proposes, comprises the following steps:
S1, under the conditions of ice-water bath, by weight by 15-25 part γ-aminoethylaminopropyl trimethoxy silane,
1-2 part N, N-dimethyl cyclohexyl amine and 20-40 part oxolane add in reaction vessel, add after stirring and dissolving
2-5 part dichloro-phenyl phosphate, is warming up to 45-55 DEG C after reaction 2.5-4h, filters after stirring reaction 2-6h, will
Filtrate rotation obtains P-N-Si fire retardant through neutral alumina column purifying after steaming；
S2, by weight by 5-15 part expansible graphite, 2-10 part zinc stannate, 3-15 part P-N-Si fire retardant,
10-25 part attapulgite, 5-20 part montmorillonite, 3-20 part hollow glass micropearl, 10-20 part nanometer titanium dioxide
Titanium, 2-15 part expanded vermiculite, 2-15 part Graphene, 2-5 part pentaerythrite, 3-15 part anilinomethyl three ethoxy
Base silane mixes and obtains compound material；
S3, by weight 30-50 part PPG is combined material with 20-45 part and mixes,
1-2.5h, then ultrasonic disperse 20-50min is stirred, in the protection of nitrogen under the rotating speed of 2000-3500r/min
Lower addition 15-30 part '-diphenylmethane diisocyanate, 0.01-0.12 part stannous octoate and 30-50 part butanone, rise
Temperature stirs reaction 35-50min after 60-70 DEG C, adds 1-3.5 part trihydroxy methyl after being then cooled to 50-55 DEG C
Propane and 2-5 part dibromoneopentyl glycol, stir 20-50min under the rotating speed of 2500-3500r/min, then add
Enter 5-20 part epoxy resin, 5-20 part acrylic resin, 3-5 part dimethythiotoluene diamine, 1-5 part 4,4 '-
Methylene-bis-o-chloroaniline, stirs 30-50min under the rotating speed of 1000-2000r/min, is subsequently poured into mould
In, at 110-125 DEG C, solidify 2-4h after drying box is drained solvent, be down to room temperature after taking-up and obtain described
High flame-retardant polyurethane composite.
Preferably, in S1, under the conditions of ice-water bath, by weight by 20-25 part γ-aminoethylaminopropyl
Trimethoxy silane, 1.3-1.7 part N, N-dimethyl cyclohexyl amine and 28-35 part oxolane add reaction vessel
In, add 3.5-4.2 part dichloro-phenyl phosphate after stirring and dissolving, after reaction 3.2-3.8h, be warming up to 50-55 DEG C,
Filter after stirring reaction 3.5-4.5h, obtain P-N-Si through neutral alumina column purifying after filtrate rotation being steamed fire-retardant
Agent.
Preferably, in S2, expansible graphite, zinc stannate, P-N-Si fire retardant, attapulgite, illiteracy are de-
Soil, hollow glass micropearl, nano titanium oxide, expanded vermiculite, Graphene, pentaerythrite, anilinomethyl
The weight ratio of triethoxysilane is 9-13:5-9:8-13:18-22:10-18:9-15:12-18:7-11:
8-13:3.2-4:9-13.
Preferably, in S3, by weight 38-45 part PPG is combined material with 30-40 part and mixes
Uniformly, under the rotating speed of 2800-3200r/min, stir 1.5-2.1h, then ultrasonic disperse 30-40min,
21-26 part '-diphenylmethane diisocyanate, 0.07-0.11 part stannous octoate and 38-45 is added under the protection of nitrogen
Part butanone, stirring reaction 40-45min after being warming up to 64-68 DEG C, add 2-3 part after being then cooled to 52-55 DEG C
Trimethylolpropane and 3-3.6 part dibromoneopentyl glycol, stir under the rotating speed of 3000-3200r/min
30-40min, is subsequently adding 12-15 part epoxy resin, 8-15 part acrylic resin, 3.5-4.3 part dimethyl sulfide
Base toluenediamine, 3.2-4 part 4,4 '-methylene-bis-o-chloroaniline, under the rotating speed of 1400-1800r/min
Stirring 38-47min, is subsequently poured in mould, 118-121 DEG C at solidifies after draining solvent in drying box
3.2-3.8h, is down to room temperature and obtains described high flame-retardant polyurethane composite after taking-up.
Preferably, the preparation method of described high fire-retardance modified polyurethane composite, comprise the following steps:
S1, under the conditions of ice-water bath, by weight by 22 parts of γ-aminoethylaminopropyl trimethoxy silane, 1.5
Part N, N-dimethyl cyclohexyl amine and 30 parts of oxolanes add in reaction vessels, add 4.2 part two after stirring and dissolving
Chlorine phenyl phosphate, is warming up to 53 DEG C after reaction 3.5h, filters after stirring reaction 4h, after filtrate rotation being steamed in warp
Property alumina column purify obtain P-N-Si fire retardant；
S2, by weight by 10 parts of expansible graphites, 8 parts of zinc stannate, 12 parts of P-N-Si fire retardants, 20 parts recessed
Convex rod soil, 15 parts of montmorillonites, 13 parts of hollow glass micropearls, 16 parts of nano titanium oxides, 10 parts of expanded vermiculites,
12 parts of Graphenes, 3.6 parts of pentaerythrites, 12 parts of anilinomethyl triethoxysilanes mix and obtain compound
Material；
S3, by weight 42 parts of PPGs and 35 parts of compound materials are mixed, 3000r/min's
Stir 2h, then ultrasonic disperse 35min under rotating speed, under the protection of nitrogen, add 22 parts of diphenyl-methane two isocyanides
Acid esters, 0.1 part of stannous octoate and 42 parts of butanone, after being warming up to 65 DEG C, stirring reaction 42min, is then cooled to
Add 2.6 parts of trimethylolpropanes and 3.3 parts of dibromoneopentyl glycols after 55 DEG C, stir under the rotating speed of 3100r/min
Mix 38min, be subsequently adding 13.5 parts of epoxy resin, 12.5 parts of acrylic resins, 4.2 parts of dimethyl sulphur-based toluene
Diamines, 3.8 part 4,4 '-methylene-bis-o-chloroaniline, under the rotating speed of 1600r/min stir 45min, so
After pour in mould, drain in drying box at 120 DEG C, solidify 3.5h after solvent, be down to room temperature after taking-up and obtain
To described high flame-retardant polyurethane composite.
Preferably, in S2, described expanded vermiculite is modified expanded vermiculite, and described modified expanded vermiculite is adopted
Modifying agent be DTAB, TTAB, cetyl front three
Base ammonium bromide, Cetyltrimethylammonium bromide, stearyl dimethyl benzyl ammonium chloride, docosyl
One or more mixture in trimethyl ammonium chloride.
Preferably, in S3, described PPG is PPG N220, PPG N330,
One or more mixture in PPG 3050.
In the preparation process of high fire-retardance modified polyurethane composite, first with γ-aminoethylaminopropyl front three
TMOS and dichloro-phenyl phosphate are raw material, and the condition reacted by control makes γ-aminoethylaminopropyl three
Amino in methoxy silane there occurs nucleophilic substitution with the chlorine in dichloro-phenyl phosphate, thus by γ-ammonia
Ethylaminopropyl trimethoxy silane and dichloro-phenyl phosphate are combined as a whole, and have obtained P-N-Si fire retardant,
By itself and expansible graphite, zinc stannate, attapulgite, montmorillonite, hollow glass micropearl, nanometer titanium dioxide
After titanium, expanded vermiculite, Graphene mix according to the above ratio, P-N-Si fire retardant and anilinomethyl triethoxy
Silane can react with the active group of each filling surface, and the character improving each filling surface is answered
Close filler；With PPG, '-diphenylmethane diisocyanate as urethane monomer, by controlling monomer
Ratio so as to get base polyurethane prepolymer for use as have excellent mechanical property, hydrolytic resistance, heat resistance and resistance to always
The property changed, add dibromoneopentyl glycol coordinates as chain extender with trimethylolpropane, thus by ignition-proof element
Bromine atoms introduces in polyurethane, and adds compounded mix and be modified it, and wherein, P-N-Si is fire-retardant
Agent, during decomposing, can generate the carbonaceous protective layer of one layer of Si-O and Si-C, discharges nitrogen, little simultaneously
Expansible graphite in the non-flammable gases such as molecular water, with system, zinc stannate, attapulgite, montmorillonite,
Hollow glass micropearl, expanded vermiculite, Graphene, pentaerythrite, anilinomethyl triethoxysilane and dibromo
Neopentyl glycol and dimethythiotoluene diamine, 4,4 '-methylene-bis-o-chloroaniline has synergy,
Significantly improve anti-flammability and the smoke-suppressing of composite；Add epoxy resin and it is entered by acrylic resin
Row modification, improves pliability and the impact resistance of compound polyurethane material.
Detailed description of the invention
Below, by specific embodiment, technical scheme is described in detail.
Embodiment 1
The preparation method of a kind of high fire-retardance modified polyurethane composite that the present invention proposes, comprises the following steps:
S1, under the conditions of ice-water bath, by weight by 15 parts of γ-aminoethylaminopropyl trimethoxy silane, 2
Part N, N-dimethyl cyclohexyl amine and 20 parts of oxolanes add in reaction vessels, add 5 parts of dichloros after stirring and dissolving
Phenyl phosphate, is warming up to 55 DEG C after reaction 2.5h, filters, through neutrality after filtrate rotation being steamed after stirring reaction 2h
Alumina column purifies and obtains P-N-Si fire retardant；
S2, by weight by 15 parts of expansible graphites, 2 parts of zinc stannate, 15 parts of P-N-Si fire retardants, 10 parts recessed
Convex rod soil, 20 parts of montmorillonites, 3 parts of hollow glass micropearls, 20 parts of nano titanium oxides, 2 parts of expanded vermiculites,
15 parts of Graphenes, 2 parts of pentaerythrites, 15 parts of anilinomethyl triethoxysilanes mix and obtain compound material；
S3, by weight 50 parts of PPGs and 20 parts of compound materials are mixed, 3500r/min's
Stir 1h, then ultrasonic disperse 50min under rotating speed, under the protection of nitrogen, add 15 parts of diphenyl-methane two isocyanides
Acid esters, 0.12 part of stannous octoate and 30 parts of butanone, after being warming up to 70 DEG C, stirring reaction 35min, is then cooled to
Add 1 part of trimethylolpropane and 5 parts of dibromoneopentyl glycols after 55 DEG C, stir under the rotating speed of 2500r/min
50min, be subsequently adding 5 parts of epoxy resin, 20 parts of acrylic resins, 3 parts of dimethythiotoluene diamines, 5 parts
4,4 '-methylene-bis-o-chloroaniline, under the rotating speed of 1000r/min, stir 50min, be subsequently poured in mould,
At 110 DEG C, solidify 4h after draining solvent in drying box, be down to room temperature after taking-up and obtain the poly-ammonia of described high fire-retardance
Ester composite.
Embodiment 2
The preparation method of a kind of high fire-retardance modified polyurethane composite that the present invention proposes, comprises the following steps:
S1, under the conditions of ice-water bath, by weight by 25 parts of γ-aminoethylaminopropyl trimethoxy silane, 1
Part N, N-dimethyl cyclohexyl amine and 40 parts of oxolanes add in reaction vessels, add 2 parts of dichloros after stirring and dissolving
Phenyl phosphate, is warming up to 45 DEG C after reaction 4h, filters, through neutral oxygen after filtrate rotation being steamed after stirring reaction 6h
Change aluminium post purifying and obtain P-N-Si fire retardant；
S2, by weight by 5 parts of expansible graphites, 10 parts of zinc stannate, 3 parts of P-N-Si fire retardants, 25 parts recessed
Convex rod soil, 5 parts of montmorillonites, 20 parts of hollow glass micropearls, 10 parts of nano titanium oxides, 15 parts of expanded vermiculites,
2 parts of Graphenes, 5 parts of pentaerythrites, 3 parts of anilinomethyl triethoxysilanes mix and obtain compound material；
S3, by weight 30 parts of PPGs and 45 parts of compound materials are mixed, 2000r/min's
Stir 2.5h, then ultrasonic disperse 20min under rotating speed, under the protection of nitrogen, add 30 parts of diphenyl-methanes two different
Cyanate, 0.01 part of stannous octoate and 50 parts of butanone, after being warming up to 60 DEG C, stirring reaction 50min, then lowers the temperature
After 50 DEG C, add 3.5 parts of trimethylolpropanes and 2 parts of dibromoneopentyl glycols, stir under the rotating speed of 3500r/min
Mix 20min, be subsequently adding 20 parts of epoxy resin, 5 parts of acrylic resins, 5 parts of dimethythiotoluene diamines, 1
Part 4,4 '-methylene-bis-o-chloroaniline, stirs 30min under the rotating speed of 2000r/min, is subsequently poured into mould
In, at 125 DEG C, solidify 2h after drying box is drained solvent, be down to room temperature after taking-up and obtain described high fire-retardance
Compound polyurethane material.
Embodiment 3
The preparation method of a kind of high fire-retardance modified polyurethane composite that the present invention proposes, comprises the following steps:
S1, under the conditions of ice-water bath, by weight by 20 parts of γ-aminoethylaminopropyl trimethoxy silane, 1.7
Part N, N-dimethyl cyclohexyl amine and 28 parts of oxolanes add in reaction vessels, add 4.2 part two after stirring and dissolving
Chlorine phenyl phosphate, is warming up to 55 DEG C after reaction 3.2h, filters, warp after filtrate rotation being steamed after stirring reaction 3.5h
Neutral alumina column purifies and obtains P-N-Si fire retardant；
S2, by weight by 13 parts of expansible graphites, 5 parts of zinc stannate, 13 parts of P-N-Si fire retardants, 18 parts recessed
Convex rod soil, 18 parts of montmorillonites, 9 parts of hollow glass micropearls, 18 parts of nano titanium oxides, 7 parts of expanded vermiculites,
13 parts of Graphenes, 3.2 parts of pentaerythrites, 13 parts of anilinomethyl triethoxysilanes mix and obtain compound
Material；
S3, by weight by many to 10 parts of PPG N220,20 parts of PPG N330,15 parts of polyethers
Unit's alcohol 3050 mixes with 30 parts of compound materials, stirs 1.5h under the rotating speed of 3200r/min, the most ultrasonic
Dispersion 40min, under the protection of nitrogen add 26 parts of '-diphenylmethane diisocyanates, 0.07 part of stannous octoate and
45 parts of butanone, stirring reaction 45min after being warming up to 64 DEG C, add 2 parts of trihydroxy methyls after being then cooled to 55 DEG C
Propane and 3.6 parts of dibromoneopentyl glycols, stir 40min under the rotating speed of 3000r/min, be subsequently adding 12 parts of rings
Epoxy resins, 15 parts of acrylic resins, 3.5 parts of dimethythiotoluene diamines, 4 parts of 4,4 '-di-2-ethylhexylphosphine oxide neighbour's chlorine
Aniline, stirs 38min under the rotating speed of 1800r/min, is subsequently poured in mould, drains molten in drying box
At 121 DEG C, solidify 3.2h after agent, be down to room temperature after taking-up and obtain described high flame-retardant polyurethane composite.
Embodiment 4
The preparation method of a kind of high fire-retardance modified polyurethane composite that the present invention proposes, comprises the following steps:
S1, under the conditions of ice-water bath, by weight by 25 parts of γ-aminoethylaminopropyl trimethoxy silane, 1.3
Part N, N-dimethyl cyclohexyl amine and 35 parts of oxolanes add in reaction vessels, add 3.5 part two after stirring and dissolving
Chlorine phenyl phosphate, is warming up to 50 DEG C after reaction 3.8h, filters, warp after filtrate rotation being steamed after stirring reaction 4.5h
Neutral alumina column purifies and obtains P-N-Si fire retardant；
S2, by weight by 9 parts of expansible graphites, 9 parts of zinc stannate, 8 parts of P-N-Si fire retardants, 22 parts concavo-convex
Rod soil, 10 parts of montmorillonites, 15 parts of hollow glass micropearls, 12 parts of nano titanium oxides, 11 parts of expanded vermiculites, 8
Part Graphene, 4 parts of pentaerythrites, 9 parts of anilinomethyl triethoxysilanes mix and obtain compound material；
Described expanded vermiculite is modified expanded vermiculite, and the modifying agent that described modified expanded vermiculite is used is myristyl
Trimethylammonium bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide are by weight
The mixture of 3:4:1；
S3, by weight by 18 parts of PPG N330,20 parts of PPGs 3050 and 40 parts of compounds
Material mixes, and stirs 2.1h, then ultrasonic disperse 30min, at nitrogen under the rotating speed of 2800r/min
Protection is lower adds 21 parts of '-diphenylmethane diisocyanates, 0.11 part of stannous octoate and 38 parts of butanone, is warming up to 68 DEG C
Rear stirring reaction 40min, adds 3 parts of trimethylolpropanes and 3 parts of dibromoneopentyl glycols after being then cooled to 52 DEG C,
Under the rotating speed of 3200r/min, stir 30min, be subsequently adding 15 parts of epoxy resin, 8 parts of acrylic resins, 4.3
Part dimethythiotoluene diamine, 3.2 part 4,4 '-methylene-bis-o-chloroaniline, under the rotating speed of 1400r/min
Stirring 47min, is subsequently poured in mould, solidifies 3.8h, take in drying box after draining solvent at 118 DEG C
It is down to room temperature after going out and obtains described high flame-retardant polyurethane composite.
Embodiment 5
The preparation method of a kind of high fire-retardance modified polyurethane composite that the present invention proposes, comprises the following steps:
S1, under the conditions of ice-water bath, by weight by 22 parts of γ-aminoethylaminopropyl trimethoxy silane, 1.5
Part N, N-dimethyl cyclohexyl amine and 30 parts of oxolanes add in reaction vessels, add 4.2 part two after stirring and dissolving
Chlorine phenyl phosphate, is warming up to 53 DEG C after reaction 3.5h, filters after stirring reaction 4h, after filtrate rotation being steamed in warp
Property alumina column purify obtain P-N-Si fire retardant；
S2, by weight by 10 parts of expansible graphites, 8 parts of zinc stannate, 12 parts of P-N-Si fire retardants, 20 parts recessed
Convex rod soil, 15 parts of montmorillonites, 13 parts of hollow glass micropearls, 16 parts of nano titanium oxides, 10 parts of expanded vermiculites,
12 parts of Graphenes, 3.6 parts of pentaerythrites, 12 parts of anilinomethyl triethoxysilanes mix and obtain compound
Material；Described expanded vermiculite is modified expanded vermiculite, and the modifying agent that described modified expanded vermiculite is used is 12
Alkyl trimethyl ammonium bromide；
S3, by weight 42 parts of PPG N220 and 35 parts of compound materials are mixed,
Stir 2h, then ultrasonic disperse 35min under the rotating speed of 3000r/min, under the protection of nitrogen, add 22 part two
Phenylmethane diisocyanate, 0.1 part of stannous octoate and 42 parts of butanone, stirring reaction 42min after being warming up to 65 DEG C,
Then 2.6 parts of trimethylolpropanes and 3.3 parts of dibromoneopentyl glycols are added after being cooled to 55 DEG C, at 3100r/min
Rotating speed under stir 38min, be subsequently adding 13.5 parts of epoxy resin, 12.5 parts of acrylic resins, 4.2 part two
(methylthiomethyl) diamines, 3.8 part 4,4 '-methylene-bis-o-chloroaniline, under the rotating speed of 1600r/min stir
45min, is subsequently poured in mould, solidifies 3.5h, after taking-up in drying box after draining solvent at 120 DEG C
It is down to room temperature and obtains described high flame-retardant polyurethane composite.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art is in the technical scope that the invention discloses, according to this
The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention
Within the scope of.
Claims (7)
1. the preparation method of a high fire-retardance modified polyurethane composite, it is characterised in that include following step
Rapid:
S1, under the conditions of ice-water bath, by weight by 15-25 part γ-aminoethylaminopropyl trimethoxy silane,
1-2 part N, N-dimethyl cyclohexyl amine and 20-40 part oxolane add in reaction vessel, add after stirring and dissolving
2-5 part dichloro-phenyl phosphate, is warming up to 45-55 DEG C after reaction 2.5-4h, filters after stirring reaction 2-6h, will
Filtrate rotation obtains P-N-Si fire retardant through neutral alumina column purifying after steaming；
S2, by weight by 5-15 part expansible graphite, 2-10 part zinc stannate, 3-15 part P-N-Si fire retardant,
10-25 part attapulgite, 5-20 part montmorillonite, 3-20 part hollow glass micropearl, 10-20 part nanometer titanium dioxide
Titanium, 2-15 part expanded vermiculite, 2-15 part Graphene, 2-5 part pentaerythrite, 3-15 part anilinomethyl three ethoxy
Base silane mixes and obtains compound material；
S3, by weight 30-50 part PPG is combined material with 20-45 part and mixes,
1-2.5h, then ultrasonic disperse 20-50min is stirred, in the protection of nitrogen under the rotating speed of 2000-3500r/min
Lower addition 15-30 part '-diphenylmethane diisocyanate, 0.01-0.12 part stannous octoate and 30-50 part butanone, rise
Temperature stirs reaction 35-50min after 60-70 DEG C, adds 1-3.5 part trihydroxy methyl after being then cooled to 50-55 DEG C
Propane and 2-5 part dibromoneopentyl glycol, stir 20-50min under the rotating speed of 2500-3500r/min, then add
Enter 5-20 part epoxy resin, 5-20 part acrylic resin, 3-5 part dimethythiotoluene diamine, 1-5 part 4,4 '-
Methylene-bis-o-chloroaniline, stirs 30-50min under the rotating speed of 1000-2000r/min, is subsequently poured into mould
In, at 110-125 DEG C, solidify 2-4h after drying box is drained solvent, be down to room temperature after taking-up and obtain described
High flame-retardant polyurethane composite.
The most according to claim 1, the preparation method of high fire-retardance modified polyurethane composite, its feature exists
In, in S1, under the conditions of ice-water bath, by weight by 20-25 part γ-aminoethylaminopropyl trimethoxy
Silane, 1.3-1.7 part N, N-dimethyl cyclohexyl amine and 28-35 part oxolane add in reaction vessel, stirring
Adding 3.5-4.2 part dichloro-phenyl phosphate after dissolving, be warming up to 50-55 DEG C after reaction 3.2-3.8h, stirring is anti-
Filter after answering 3.5-4.5h, purify through neutral alumina column after filtrate rotation is steamed and obtain P-N-Si fire retardant.
The preparation method of high fire-retardance modified polyurethane composite the most according to claim 1 or claim 2, its feature
It is, in S2, expansible graphite, zinc stannate, P-N-Si fire retardant, attapulgite, montmorillonite, sky
Heart glass microballoon, nano titanium oxide, expanded vermiculite, Graphene, pentaerythrite, anilinomethyl three ethoxy
The weight ratio of base silane is 9-13:5-9:8-13:18-22:10-18:9-15:12-18:7-11:8-13:
3.2-4:9-13.
4. according to the preparation method of high fire-retardance modified polyurethane composite according to any one of claim 1-3,
It is characterized in that, in S3, by weight 38-45 part PPG is combined material with 30-40 part and mixes
Uniformly, under the rotating speed of 2800-3200r/min, stir 1.5-2.1h, then ultrasonic disperse 30-40min,
21-26 part '-diphenylmethane diisocyanate, 0.07-0.11 part stannous octoate and 38-45 is added under the protection of nitrogen
Part butanone, stirring reaction 40-45min after being warming up to 64-68 DEG C, add 2-3 after being then cooled to 52-55 DEG C
Part trimethylolpropane and 3-3.6 part dibromoneopentyl glycol, stir under the rotating speed of 3000-3200r/min
30-40min, is subsequently adding 12-15 part epoxy resin, 8-15 part acrylic resin, 3.5-4.3 part dimethyl sulfide
Base toluenediamine, 3.2-4 part 4,4 '-methylene-bis-o-chloroaniline, under the rotating speed of 1400-1800r/min
Stirring 38-47min, is subsequently poured in mould, 118-121 DEG C at solidifies after draining solvent in drying box
3.2-3.8h, is down to room temperature and obtains described high flame-retardant polyurethane composite after taking-up.
5. according to the preparation method of high fire-retardance modified polyurethane composite according to any one of claim 1-4,
It is characterized in that, comprise the following steps:
S1, under the conditions of ice-water bath, by weight by 22 parts of γ-aminoethylaminopropyl trimethoxy silane, 1.5
Part N, N-dimethyl cyclohexyl amine and 30 parts of oxolanes add in reaction vessels, add 4.2 part two after stirring and dissolving
Chlorine phenyl phosphate, is warming up to 53 DEG C after reaction 3.5h, filters after stirring reaction 4h, after filtrate rotation being steamed in warp
Property alumina column purify obtain P-N-Si fire retardant；
S2, by weight by 10 parts of expansible graphites, 8 parts of zinc stannate, 12 parts of P-N-Si fire retardants, 20 parts recessed
Convex rod soil, 15 parts of montmorillonites, 13 parts of hollow glass micropearls, 16 parts of nano titanium oxides, 10 parts of expanded vermiculites,
12 parts of Graphenes, 3.6 parts of pentaerythrites, 12 parts of anilinomethyl triethoxysilanes mix and obtain compound
Material；
S3, by weight 42 parts of PPGs and 35 parts of compound materials are mixed, at 3000r/min
Rotating speed under stir 2h, then ultrasonic disperse 35min, under the protection of nitrogen add 22 parts of diphenyl-methanes two different
Cyanate, 0.1 part of stannous octoate and 42 parts of butanone, after being warming up to 65 DEG C, stirring reaction 42min, then lowers the temperature
2.6 parts of trimethylolpropanes and 3.3 parts of dibromoneopentyl glycols are added, under the rotating speed of 3100r/min after 55 DEG C
Stirring 38min, is subsequently adding 13.5 parts of epoxy resin, 12.5 parts of acrylic resins, 4.2 parts of dimethyl sulphur-based first
Phenylenediamine, 3.8 part 4,4 '-methylene-bis-o-chloroaniline, under the rotating speed of 1600r/min stir 45min,
It is subsequently poured in mould, at 120 DEG C, solidifies 3.5h after drying box is drained solvent, after taking-up, be down to room temperature
Obtain described high flame-retardant polyurethane composite.
6. according to the preparation method of high fire-retardance modified polyurethane composite according to any one of claim 1-5,
It is characterized in that, in S2, described expanded vermiculite is modified expanded vermiculite, and described modified expanded vermiculite is adopted
Modifying agent be DTAB, TTAB, cetyl front three
Base ammonium bromide, Cetyltrimethylammonium bromide, stearyl dimethyl benzyl ammonium chloride, docosyl
One or more mixture in trimethyl ammonium chloride.
7. according to the preparation method of high fire-retardance modified polyurethane composite according to any one of claim 1-6,
It is characterized in that, in S3, described PPG is PPG N220, PPG N330,
One or more mixture in PPG 3050.
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| CN112647358A (en) * | 2020-12-07 | 2021-04-13 | 静宁县恒达有限责任公司 | Phosphorus-boron hybrid chain prepolymer block polyurethane water-based moisture-proof flame-retardant carton film coating agent and preparation method and application thereof |
| CN114213807A (en) * | 2021-12-15 | 2022-03-22 | 天津大学 | High-thermal-stability intumescent compound flame retardant modified epoxy resin material and preparation method thereof |
| CN114213807B (en) * | 2021-12-15 | 2023-06-27 | 天津大学 | High-thermal-stability intumescent flame retardant modified epoxy resin material and preparation method thereof |
| CN114603964A (en) * | 2022-03-14 | 2022-06-10 | 浙江汇锋智造科技有限公司 | High-barrier composite new material and production process thereof |
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Application publication date: 20160817 |