CN107815088A - A kind of flame-retardant polyurethane and preparation method thereof - Google Patents
A kind of flame-retardant polyurethane and preparation method thereof Download PDFInfo
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- CN107815088A CN107815088A CN201610824849.XA CN201610824849A CN107815088A CN 107815088 A CN107815088 A CN 107815088A CN 201610824849 A CN201610824849 A CN 201610824849A CN 107815088 A CN107815088 A CN 107815088A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C08K5/00—Use of organic ingredients
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- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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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
- C08L75/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The present invention provides a kind of flame-retardant polyurethane and preparation method thereof, the flame-retardant polyurethane includes composite flame-retardant agent and polyurethane, the composite flame-retardant agent includes brominated flame-retardant and sulfur-bearing fire retardant and/or phosphonium flame retardant, and the brominated flame-retardant is brominated phenolic compound and its epoxy resin.Brominated flame-retardant has synergy with sulfur-bearing fire retardant and/or phosphonium flame retardant on flame retardant effect, the fire resistance of composite flame-retardant agent can be strengthened, therefore the fire resistance of the polyurethane finally given is strengthened, and make it that the flame-retardant polyurethane of the present invention there is good mechanical performance and heat resistance, be a kind of polyurethane with larger economy and environmentally friendly friendly.
Description
Technical field
The invention belongs to fire proofing field, is related to a kind of flame-retardant polyurethane and preparation method thereof.
Background technology
Using mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with air-conditioning, refrigerator, television image, sound
The various products that articles for use etc. use for the family expenses of representative, office electric equipment products and other field are rung, for safety, significant portion
Product require that it possesses different degrees of fire resistance.
In order that product reaches required fire resistance or grade, traditional technology usually uses to be added into material system
Add halogen-containing fire retardant matter, for example, into system material addition as deca-BDE, tetrabromobisphenol A, tetrabromo dipentaerythritol,
The brominated amount such as Brominated Polystyrene, pentabromotoluene or HBCD is higher or containing the higher organic chemistry of halogen quantity
Material, although these halogen-containing fire retardant matter anti-flammabilitys are preferable, its usage amount is bigger, such as the system in engineering plastics
In standby, in order to reach preferable flame retardant effect, during using brominated fire retardant, it is ensured that in engineering plastics bromine content 20% with
On, this causes bromo element content in product higher, and content of halogen height also brings along some detrimental effects in product, such as
The harmful substance such as dioxin organic halogen chemical contamination environment of difficult degradation can be produced when high temperature or burning, influences the mankind
And animal health.
Therefore, the usage amount and can for how reducing fire retardant enough ensures the problem of flame retardant effect is this area urgent need to resolve.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of flame-retardant polyurethane and preparation method thereof.
To use following technical scheme up to this purpose, the present invention：
On the one hand, the present invention provides a kind of flame-retardant polyurethane, and the flame-retardant polyurethane includes composite flame-retardant agent and gathered
Urethane, the composite flame-retardant agent include brominated flame-retardant and sulfur-bearing fire retardant and/or phosphonium flame retardant, the brominated flame-retardant
For brominated phenolic compound and its epoxy resin.
Coordinate sulfur-bearing fire retardant and/or phosphonium flame retardant using brominated flame-retardant in the fire-proof resin composition of the present invention
Synergistic flame retardant is formed, then the polyurethane plastics for coordinating polyurethane its composition can be prepared has good anti-flammability
With good mechanical performance.
Brominated flame-retardant must be included in the composite flame-retardant agent of the present invention, and for sulfur-bearing fire retardant and phosphonium flame retardant
Can include one of which can also the two be included in composite flame-retardant agent, it is preferable that the composite flame-retardant agent include it is brominated
Fire retardant, sulfur-bearing fire retardant and phosphonium flame retardant, the brominated flame-retardant are brominated phenolic compound and its epoxy resin.
Preferably, weight percent content shared by brominated flame-retardant is less than 10% in the flame-retardant polyurethane, such as
10%th, 9%, 8.5%, 8%, 7%, 7.5%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, 0.1% etc., it is excellent
Select 1-5%.
Preferably, weight percent content shared by sulfur-bearing fire retardant is more than 0.2% in the flame-retardant polyurethane, such as
0.2%th, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 1.8%, 2% etc.,
It is preferred that 0.2-1%.
Preferably, weight percent content shared by phosphonium flame retardant is more than 0.2% in the flame-retardant polyurethane, such as
0.2%th, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 1.8%, 2%,
2.5%th, 3%, 4%, 5% etc., preferably 0.2-2%.
In the content range of brominated flame-retardant, sulfur-bearing fire retardant and phosphonium flame retardant that the present invention limits, brominated resistance
Fire agent and sulfur-bearing fire retardant and/or phosphonium flame retardant are mutually coordinated, collaboration enhancing fire resistance, can either ensure that polyurethane has
Preferable fire resistance, and can is enough to control bromo element content in relatively low scope, so as to reduce because high temperature produces harmful substance
Possibility, and in the content range, the various aspects of performance for the flame-retardant polyurethane being prepared can be optimized, and be had
Good mechanical performance and fire resistance and heat resistance.
Traditional brominated flame-retardant will keep bromo element content just to be played more than 20% when being applied in engineering material
Preferable flame retardant effect, to ensure the fire resistance of polyurethane, the present invention on the basis of brominated flame-retardant by adding on a small quantity
Sulfur-bearing fire retardant and/or phosphonium flame retardant composition composite flame-retardant agent, can cause brominated flame-retardant and sulfur-bearing fire retardant and/or
The flame retardant effect of phosphonium flame retardant is mutually promoted, and reaches the effect of cooperative flame retardant, while reduces the usage amount of brominated flame-retardant,
It is cost-effective, and can ensure that polyurethane has good mechanical performance.
In the present invention, each component content is using the gross weight of flame-retardant polyurethane as 100% in flame-retardant polyurethane
Calculate.
Preferably, the brominated flame-retardant is brominated phenolic resin, bromination novolac epoxy resin, brominated bisphenol A, bromination pair
In phenol A derivatives, brominated bisphenol a type epoxy resin, tetrabromo-bisphenol s, tetrabromobisphenol allyl ether, tribromphenol or pentabromophenol
Any one or at least two combination, preferably brominated bisphenol A, brominated bisphenol A derivatives or brominated bisphenol a type epoxy resin.
Preferably, the sulfur-bearing fire retardant is to diphenyl disulfide phenol and/or 4,4'- diaminourea diphenyl disulfide, preferred pair benzene
Dithiol.
Preferably, the phosphonium flame retardant is that DOPO is etherified bisphenol-A, DOPO modified epoxies, three (2,6- dimethyl benzenes
Base) it is phosphine, four-(2,6- xylyls) resorcinol biphosphonates, resorcinol tetraphenyldiphosphate, triphenyl phosphate, double
Phenol A double (diphenyl phosphoester), phosphonitrile fire retardant, 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxygen
Compound, 10- (2,5- dihydroxy naphthyl) -10- hydrogen -9- oxa-s -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- of 9,10- dihydro-9-oxies
In phospho hetero phenanthrene -10- oxide fire retardants any one or at least two mixture.
Other fire proofings can be added as needed in the composite flame-retardant agent of the present invention.
Preferably, other described fire proofings be organic silicon fibre retardant, chloride organic fire-retardant, nitrogenous organic fire-retardant or
In inorganic combustion inhibitor any one or at least two combination.
Preferably, the chloride organic fire-retardant is Dioctyl Tetrachlorophthalate, chlorendic anhydride, chlorine mattress acid or tetrachloro
In bisphenol-A any one or at least two combination.
Preferably, the nitrogenous organic fire-retardant be dicyandiamide, biruea or melamine in any one or at least
Two kinds of combination.
Preferably, the inorganic combustion inhibitor is any one in aluminium hydroxide, magnesium hydroxide, antimony oxide or Firebrake ZB
Kind or at least two combination.
Preferably, polyurethane accounts for 80-95% in the flame-retardant polyurethane, such as 80%,
83%th, 85%, 88%, 90%, 92%, 94% or 95%.
Heat-proof modifier of the flame-retardant polyurethane also comprising percentage by weight for 1-3%, such as heat-proof modifier
Content can be 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8% or 3%.
Preferably, the heat-proof modifier is N-2,6- 3,5-dimethylphenyl maleimide heat-proof modifying agent.
Preferably, the antioxidant in the flame-retardant polyurethane also comprising percentage by weight for 1-3%, such as antioxidant
Content can be 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8% or 3%.
Preferably, the antioxidant in antioxidant 1010, irgasfos 168 or antioxidant 1076 any one or extremely
Few two kinds combination.
Second aspect, the invention provides the preparation method of flame-retardant polyurethane as described in relation to the first aspect, methods described
For：The composite flame-retardant agent, polyurethane particles, heat-proof modifier and antioxidant are well mixed, then extruding pelletization obtains institute
State flame-retardant polyurethane.
Preferably, described be blended in high pressure homogenizer mixes, the mixing temperature be 60-80 DEG C (such as 62 DEG C, 65
DEG C, 68 DEG C, 70 DEG C, 72 DEG C, 74 DEG C, 76 DEG C or 78 DEG C), incorporation time be 10-20min (such as 12min, 14min, 16min or
18min), the pressure in the high pressure homogenizer is 15-20Mpa (such as 16Mpa, 17Mpa, 18Mpa or 19Mpa)；
Preferably, the extrusion is carried out in double screw extruder, is in each section of temperature of double screw extruder：One area's temperature
170-180 DEG C (such as 170 DEG C, 173 DEG C, 175 DEG C, 178 DEG C or 180 DEG C), two 180-190 DEG C of area's temperature (such as 180 DEG C, 183
DEG C, 185 DEG C, 188 DEG C or 190 DEG C), three 210-230 DEG C of area's temperature (such as 210 DEG C, 212 DEG C, 215 DEG C, 218 DEG C, 220 DEG C,
223 DEG C, 225 DEG C, 228 DEG C or 230 DEG C), four 240-260 DEG C of area's temperature (such as 240 DEG C, 243 DEG C, 245 DEG C, 248 DEG C, 250
DEG C, 253 DEG C, 255 DEG C, 258 DEG C or 260 DEG C), five 170-180 DEG C of area's temperature (such as 170 DEG C, 173 DEG C, 175 DEG C, 178 DEG C or
180℃)。
Relative to prior art, the present invention has the advantages that：
Brominated flame-retardant and sulfur-bearing fire retardant in the fire-proof resin composition contained in the flame-retardant polyurethane of the present invention
And/or phosphonium flame retardant has synergy on flame retardant effect, the fire resistance of polyurethane can be strengthened, and cause the present invention
Polyurethane there is good mechanical performance and heat resistance.The bending strength for the polyurethane that the present invention is prepared may be up to 80-
85MPa, tensile strength are up to 65-70MPa, and notch impact strength is up to 29-35J/m, and heat distortion temperature is 130-137 DEG C, is melted
Refer to as 12-14, oxygen index (OI) 27.2-28%, there is good anti-flammability, excellent mechanical performance and heat resistance.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1
By 10g brominated bisphenol a type epoxy resin, 5g to diphenyl disulfide phenol and 80g polyurethane, 3g N-2,6- 3,5-dimethylphenyls
Maleimide amine type (TM-PMI) heat-proof modifier and 1g antioxidant 1010s mix 10min extremely in high pressure homogenizer at 70 DEG C
It is well mixed, then extruded in double screw extruder, each section of temperature of double screw extruder is：One 175 DEG C of area's temperature, two area's temperature
180 DEG C of degree, three 210 DEG C of area's temperature, four 240 DEG C of area's temperature, five 170 DEG C of area's temperature, granulation obtain polyurethane A, its performance test
As a result it is as shown in table 1.
Embodiment 2
By 10g brominated bisphenols A, 3g to diphenyl disulfide phenol and 85g polyurethane, 1g N-2,6- 3,5-dimethylphenyl maleimides
Type (TM-PMI) heat-proof modifier and 1g irgasfos 168s mix at 60 DEG C 20min to well mixed in high pressure homogenizer, and
Extruded afterwards in double screw extruder, each section of temperature of double screw extruder is：One 175 DEG C of area's temperature, two 190 DEG C of area's temperature, three
210 DEG C of area's temperature, four 260 DEG C of area's temperature, five 175 DEG C of area's temperature, granulation obtain polyurethane B, its performance test results such as institute of table 1
Show.
Embodiment 3
By 5g brominated bisphenols A, 0.2g 4,4'- diaminourea diphenyl disulfide and 90.8g polyurethane, 1gN-2,6- dimethyl
Phenyl maleimide type (TM-PMI) heat-proof modifier and 3g antioxidant 1010s mix in high pressure homogenizer at 80 DEG C
10min is then extruded, each section of temperature of double screw extruder is to being well mixed in double screw extruder：One area's temperature 180
DEG C, two 190 DEG C of area's temperature, three 210 DEG C of area's temperature, four 260 DEG C of area's temperature, five 170 DEG C of area's temperature, it is granulated and obtains polyurethane C, its
The performance test results are as shown in table 1.
Embodiment 4
By 10g brominated bisphenol a type epoxy resin, 1g tetra--(2,6- xylyls) resorcinol biphosphonate and the poly- ammonia of 84g
Ester, 2gN-2,6- 3,5-dimethylphenyl maleimide amine type (TM-PMI) heat-proof modifiers and 3g irgasfos 168s are in high pressure homogenizer
In 15min is mixed at 75 DEG C to well mixed, then extruded in double screw extruder, each section of temperature of double screw extruder
For：One 180 DEG C of area's temperature, two 190 DEG C of area's temperature, three 230 DEG C of area's temperature, four 240 DEG C of area's temperature, five 180 DEG C of area's temperature, it is granulated
Polyurethane D is obtained, its performance test results is as shown in table 1.
Embodiment 5
10g brominated bisphenols A, 1.5g DOPO are etherified bisphenol-A and 84.5g polyurethane, 3gN-2,6- 3,5-dimethylphenyls Malaysia
Imide-type (TM-PMI) heat-proof modifier and 1g antioxidant 1010s mix 20min to mixing in high pressure homogenizer at 80 DEG C
Uniformly, then extruded in double screw extruder, each section of temperature of double screw extruder is：One 170 DEG C of area's temperature, two area's temperature
190 DEG C, three 220 DEG C of area's temperature, four 250 DEG C of area's temperature, five 175 DEG C of area's temperature, it is granulated and obtains polyurethane E, its performance test knot
Fruit is as shown in table 1.
Embodiment 6
5g brominated bisphenols A, 1g DOPO are etherified bisphenol-A and 89g polyurethane, 3gN-2,6- 3,5-dimethylphenyl maleimides
Amine type (TM-PMI) heat-proof modifier and 3g antioxidant 1010s mix 10min at 70 DEG C in high pressure homogenizer and extremely mixed
It is even, then extruded in double screw extruder, each section of temperature of double screw extruder is：One 180 DEG C of area's temperature, two area's temperature 185
DEG C, three 230 DEG C of area's temperature, four 260 DEG C of area's temperature, five 180 DEG C of area's temperature, it is granulated and obtains polyurethane F, its performance test results is such as
Shown in table 1.
Embodiment 7
5g brominated bisphenols A, 0.5g DOPO are etherified bisphenol-A and 91.5g polyurethane, 1gN-2,6- 3,5-dimethylphenyls Malaysia
Imide-type (TM-PMI) heat-proof modifier and 2g antioxidant 1010s mix 15min to mixing in high pressure homogenizer at 80 DEG C
Uniformly, then extruded in double screw extruder, each section of temperature of double screw extruder is：One 175 DEG C of area's temperature, two area's temperature
180 DEG C, three 210 DEG C of area's temperature, four 240 DEG C of area's temperature, five 170 DEG C of area's temperature, it is granulated and obtains polyurethane G, its performance test knot
Fruit is as shown in table 1.
Embodiment 8
5g brominated bisphenol a type epoxy resin, 0.5g is double to diphenyl disulfide phenol, 1g tetra--(2,6- xylyls) resorcinol
Phosphate and 91.5g polyurethane, 1g N-2,6- 3,5-dimethylphenyl maleimide amine type (TM-PMI) heat-proof modifier and 1g antioxygens
Agent 168 mixes 10min to being well mixed in high pressure homogenizer at 70 DEG C, is then extruded in double screw extruder, double spiral shells
Each section of temperature of bar extruder be：One 170 DEG C of area's temperature, two 185 DEG C of area's temperature, three 220 DEG C of area's temperature, four 245 DEG C of area's temperature, five
180 DEG C of area's temperature, granulation obtain polyurethane G, and its performance test results is as shown in table 1.
Embodiment 9
5g brominated bisphenols A, 0.2g is etherified bisphenol-A and 90.3g polyurethane to diphenyl disulfide phenol, 1.5g DOPO, 3g N-2,
6- 3,5-dimethylphenyl maleimide amine type (TM-PMI) heat-proof modifiers and 1g irgasfos 168s are in high pressure homogenizer at 70 DEG C
10min is mixed to being well mixed, is then extruded in double screw extruder, each section of temperature of double screw extruder is：One area's temperature
170 DEG C, two 185 DEG C of area's temperature, three 220 DEG C of area's temperature, four 245 DEG C of area's temperature, five 180 DEG C of area's temperature, it is granulated and obtains polyurethane
H, its performance test results are as shown in table 1.
Embodiment 10
By 3g brominated bisphenol A, 1g4,4'- diaminourea diphenyl disulfide, the universal DOPO modified epoxies of 0.2g with
89.8g polyurethane, 3g N-2,6- 3,5-dimethylphenyl maleimide amine type (TM-PMI) heat-proof modifier and 3g antioxidant 1076s exist
15min is mixed to being well mixed at 70 DEG C in high pressure homogenizer, is then extruded in double screw extruder, double screw extruder
Each section of temperature be：One 170 DEG C of area's temperature, two 180 DEG C of area's temperature, three 230 DEG C of area's temperature, four 250 DEG C of area's temperature, five area's temperature
170 DEG C, granulation obtains polyurethane J, and its performance test results is as shown in table 1.
Embodiment 11
1g brominated bisphenols A, 0.5g is etherified bisphenol-A and 94.7g polyurethane, 1g N-2,6- to diphenyl disulfide phenol, 0.8gDOPO
3,5-dimethylphenyl maleimide amine type (TM-PMI) heat-proof modifier and 2g antioxidant 1076s are in high pressure homogenizer at 75 DEG C
15min is mixed to being well mixed, is then extruded in double screw extruder, each section of temperature of double screw extruder is：One area's temperature
180 DEG C, two 180 DEG C of area's temperature, three 220 DEG C of area's temperature, four 260 DEG C of area's temperature, five 180 DEG C of area's temperature, it is granulated and obtains polyurethane
K, its performance test results are as shown in table 1.
Comparative example 1
The comparative example be the difference is that only with embodiment 1, and bmminated bisphenol-A type ring is added without in the preparation of polyurethane
Oxygen tree fat and to diphenyl disulfide phenol, only by 95g polyurethane, 3gN-2,6- 3,5-dimethylphenyl maleimide amine type (TM-PMI) is heat-resisting to be changed
Polyurethane L, the performance test results such as institute of table 1 is prepared by method same as Example 1 in property agent and 1g antioxidant 1010s
Show.
Comparative example 2
The comparative example be the difference is that only with embodiment 1, and bmminated bisphenol-A type ring is added without in the preparation of polyurethane
Oxygen tree fat, the amount to diphenyl disulfide phenol of addition are 13g, the dosage and preparation method of remaining raw material with same as Example 1,
Polyurethane M is prepared, its performance test results is as shown in table 1.
Comparative example 3
The comparative example the difference is that only with embodiment 1, is added without to diphenyl disulfide phenol, adds in the preparation of polyurethane
The amount of the brominated bisphenol a type epoxy resin entered is 13g, the dosage and preparation method of remaining raw material with same as Example 1,
Polyurethane N is prepared, its performance test results is as shown in table 1.
Comparative example 4
The comparative example be the difference is that only with embodiment 4, and bmminated bisphenol-A type ring is added without in the preparation of polyurethane
Oxygen tree fat and four-(2,6- xylyl) resorcinol biphosphonates, only by 95g polyurethane, 2gN-2,6- 3,5-dimethylphenyl horses
Carry out imide-type (TM-PMI) heat-proof modifier and poly- ammonia is prepared by method same as Example 4 in 3g irgasfos 168s
Ester O, its performance test results are as shown in table 1.
Comparative example 5
The comparative example be the difference is that only with embodiment 4, and bmminated bisphenol-A type ring is added without in the preparation of polyurethane
Oxygen tree fat, the addition of four-(2,6- xylyl) resorcinol biphosphonates is 11g, the dosage of remaining raw material and preparation
Method with it is same as Example 4, polyurethane P is prepared, its performance test results is as shown in table 1.
Comparative example 6
The comparative example be the difference is that only with embodiment 4, and four-(2,6- diformazans are added without in the preparation of polyurethane
Phenyl) resorcinol biphosphonate, the addition of brominated bisphenol a type epoxy resin is 11g, the dosage of remaining raw material and preparation
Method with it is same as Example 4, polyurethane Q is prepared, its performance test results is as shown in table 1.
Comparative example 7
The comparative example be the difference is that only with embodiment 8, and bmminated bisphenol-A type ring is added without in the preparation of polyurethane
Oxygen tree fat, the dosage to diphenyl disulfide phenol is 5.5g, and remaining raw material dosage and preparation method are same as Example 8, are prepared into
It is as shown in table 1 to polyurethane Q, its performance test results.
Comparative example 8
The comparative example be the difference is that only with embodiment 8, and bmminated bisphenol-A type ring is added without in the preparation of polyurethane
Oxygen tree fat, the dosage of four-(2,6- xylyl) resorcinol biphosphonates is 6g, and remaining raw material dosage and preparation method are equal
It is same as Example 8, polyurethane S is prepared, its performance test results is as shown in table 1.
Table 1
Table 2
The bending strength for the polyurethane that the present invention is prepared up to can it can be seen from the test result of Tables 1 and 2
Up to 80-85MPa, tensile strength are up to 65-70MPa, and notch impact strength is up to 29-35J/m, heat distortion temperature 130-
137 DEG C, melting means 12-14, oxygen index (OI) 27.2-28%, therefore with good anti-flammability, excellent mechanical performance and heat-resisting
Property.
Without using brominated flame-retardant and sulfur-bearing fire retardant or individually it can be seen from embodiment 1 and comparative example 1-3 contrast
During using both fire retardants, the bending strength of its polyurethane being prepared, tensile strength and notch impact strength are obvious
Reduce, melting means increased, and oxygen index (OI) illustrates that its mechanical performance and fire resistance are decreased obviously, while also demonstrate,prove in 21-23
Bright brominated flame-retardant and sulfur-bearing fire retardant is improving the anti-flammability of polyurethane and mechanical properties with synergy.
Brominated flame-retardant and phosphonium flame retardant are improving polyurethane it can be seen from embodiment 4 and comparative example 4-6 contrast
Anti-flammability in terms of have synergy, and the addition of composite flame-retardant agent for improve mechanical performance also there is facilitation.
Equally, embodiment 8 and comparative example 7-8 contrast can also prove, sulfur-bearing fire retardant, phosphonium flame retardant and sulfur-bearing fire retardant exist
There is synergy, and the addition of composite flame-retardant agent also has for improving mechanical performance in terms of improving the anti-flammability of polyurethane
Facilitation.
Equally, the polyurethane of the present invention has higher heat it can be seen from embodiment 1-11 and comparative example 1-8 contrast
Deformation temperature, heat resistance is good, and certain influence can be produced to its heat resistance by changing its component composition.
Therefore, brominated flame-retardant can form synergistic fire retardant with sulfur-bearing fire retardant and/or phosphonium flame retardant in the present invention,
The present invention applies the synergistic fire retardant, coordinates polyurethane so that the polyurethane of preparation has good combination property, and the present invention exists
It can keep polyurethane that there is good flame-retardance energy and good mechanical performance and heat resistance while reducing bromo element content
Energy.
Applicant states that the present invention illustrates the flame-retardant polyurethane of the present invention and its preparation side by above-described embodiment
Method, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention has to rely on above-described embodiment and could implemented.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of each raw material of product of the present invention
And the addition of auxiliary element, selection of concrete mode etc., all fall within protection scope of the present invention and it is open within the scope of.
Claims (10)
1. a kind of flame-retardant polyurethane, it is characterised in that the flame-retardant polyurethane includes composite flame-retardant agent and polyurethane, described
Composite flame-retardant agent includes brominated flame-retardant and sulfur-bearing fire retardant and/or phosphonium flame retardant, and the brominated flame-retardant is brominated
Phenolic compound and its epoxy resin.
2. flame-retardant polyurethane according to claim 1, it is characterised in that brominated flame-retardant in the flame-retardant polyurethane
Shared weight percent content is less than 10%, preferably 1-5%；
Preferably, weight percent content shared by sulfur-bearing fire retardant is more than 0.2% in the flame-retardant polyurethane, preferably 0.2-
1%；
Preferably, weight percent content shared by phosphonium flame retardant is more than 0.2% in the flame-retardant polyurethane, preferably 0.2-
2%.
3. flame-retardant polyurethane according to claim 1 or 2, it is characterised in that the brominated flame-retardant is bromination phenolic aldehyde
Resin, bromination novolac epoxy resin, brominated bisphenol A, brominated bisphenol A derivatives, brominated bisphenol a type epoxy resin, tetrabromobisphenol
S, any one in tetrabromobisphenol allyl ether, tribromphenol or pentabromophenol or at least two combination, preferably brominated bisphenol
A, brominated bisphenol A derivatives or brominated bisphenol a type epoxy resin.
4. according to the flame-retardant polyurethane any one of claim 1-3, it is characterised in that the sulfur-bearing fire retardant is pair
Diphenyl disulfide phenol and/or 4,4'- diaminourea diphenyl disulfide, preferred pair diphenyl disulfide phenol；
Preferably, the phosphonium flame retardant is that DOPO is etherified bisphenol-A, DOPO modified epoxies, three (2,6- 3,5-dimethylphenyls)
Phosphine, four-(2,6- xylyls) resorcinol biphosphonates, resorcinol tetraphenyldiphosphate, triphenyl phosphate, bisphenol-A
Double (diphenyl phosphoesters), phosphonitrile fire retardant, 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxidations
Thing, 10- (2,5- dihydroxy naphthyl) -10- hydrogen -9- oxa-s -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- phosphorus of 9,10- dihydro-9-oxies
In miscellaneous phenanthrene -10- oxide fire retardants any one or at least two mixture.
5. according to the flame-retardant polyurethane any one of claim 1-4, it is characterised in that the composite flame-retardant agent also wraps
Containing other fire proofings；
Preferably, other described fire proofings are organic silicon fibre retardant, chloride organic fire-retardant, nitrogenous organic fire-retardant or inorganic
In fire retardant any one or at least two combination.
6. flame-retardant polyurethane according to claim 5, it is characterised in that the chloride organic fire-retardant is monoethyl
Diformazan dioctyl phthalate, chlorendic anhydride, chlorine mattress acid or tetrachlorobisphenol A in any one or at least two combination；
Preferably, the nitrogenous organic fire-retardant is any one in dicyandiamide, biruea or melamine or at least two
Combination；
Preferably, the inorganic combustion inhibitor be aluminium hydroxide, magnesium hydroxide, antimony oxide or Firebrake ZB in any one or
At least two combination.
7. according to the flame-retardant polyurethane any one of claim 1-6, it is characterised in that in the flame-retardant polyurethane
Polyurethane accounts for 80-95%.
8. according to the flame-retardant polyurethane any one of claim 1-7, it is characterised in that the flame-retardant polyurethane is also
Include the heat-proof modifier that percentage by weight is 1-3%；
Preferably, the heat-proof modifier is N-2,6- 3,5-dimethylphenyl maleimide heat-proof modifying agent；
Preferably, also comprising the antioxidant that percentage by weight is 1-3% in the flame-retardant polyurethane；
Preferably, the antioxidant in antioxidant 1010, irgasfos 168 or antioxidant 1076 any one or at least two
The combination of kind.
9. the preparation method of the flame-retardant polyurethane according to any one of claim 1-8, it is characterised in that methods described
For：The composite flame-retardant agent, polyurethane particles, heat-proof modifier and antioxidant are well mixed, then extruding pelletization obtains institute
State flame-retardant polyurethane.
10. preparation method according to claim 9, it is characterised in that described be blended in high pressure homogenizer mixes, described
Mixing temperature is 60-80 DEG C, incorporation time 10-20min, and the pressure in the high pressure homogenizer is 15-20Mpa；
Preferably, the extrusion is carried out in double screw extruder, is in each section of temperature of double screw extruder：One area temperature 170-
180 DEG C, two 180-190 DEG C of area's temperature, three 210-230 DEG C of area's temperature, four 240-260 DEG C of area's temperature, five area temperature 170-180
℃。
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|---|---|---|---|
| CN201610824849.XA CN107815088A (en) | 2016-09-14 | 2016-09-14 | A kind of flame-retardant polyurethane and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610824849.XA CN107815088A (en) | 2016-09-14 | 2016-09-14 | A kind of flame-retardant polyurethane and preparation method thereof |
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Family
ID=61600715
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400846A (en) * | 2018-10-27 | 2019-03-01 | 濮阳天健生物科技有限公司 | A kind of chemical reaction kettle composite insulation boards and preparation method thereof |
| CN110437421A (en) * | 2019-08-08 | 2019-11-12 | 郝立勇 | A kind of glycol modified polyurethane coating of flame retardant type phosphate ester-containing and its preparation method |
| CN114874608A (en) * | 2022-06-28 | 2022-08-09 | 满淑云 | Preparation method of heat-resistant polyurethane elastomer |
| CN115124944A (en) * | 2022-06-28 | 2022-09-30 | 广东汇齐新材料有限公司 | Heat-resistant high-fluidity thermoplastic polyurethane hot melt adhesive film and preparation method thereof |
-
2016
- 2016-09-14 CN CN201610824849.XA patent/CN107815088A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400846A (en) * | 2018-10-27 | 2019-03-01 | 濮阳天健生物科技有限公司 | A kind of chemical reaction kettle composite insulation boards and preparation method thereof |
| CN110437421A (en) * | 2019-08-08 | 2019-11-12 | 郝立勇 | A kind of glycol modified polyurethane coating of flame retardant type phosphate ester-containing and its preparation method |
| CN114874608A (en) * | 2022-06-28 | 2022-08-09 | 满淑云 | Preparation method of heat-resistant polyurethane elastomer |
| CN115124944A (en) * | 2022-06-28 | 2022-09-30 | 广东汇齐新材料有限公司 | Heat-resistant high-fluidity thermoplastic polyurethane hot melt adhesive film and preparation method thereof |
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