CN106893304A - A kind of flame-retardant polyurethane elastomer and preparation method thereof - Google Patents
A kind of flame-retardant polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN106893304A CN106893304A CN201710217526.9A CN201710217526A CN106893304A CN 106893304 A CN106893304 A CN 106893304A CN 201710217526 A CN201710217526 A CN 201710217526A CN 106893304 A CN106893304 A CN 106893304A
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08L2201/22—Halogen free composition
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention provides a kind of flame-retardant polyurethane elastomer, it is prepared from by the raw material including following mass parts：The carbon dioxide copolymer polyalcohol of 100 mass parts；The diisocyanate of 30~60 mass parts；The Corvic of 10~50 mass parts；The chain extender of 8~12 mass parts；The catalyst of 0.01~0.5 mass parts；The fire retardant of 10~40 mass parts；The heat stabilizer of 0.1~1 mass parts；The antioxidant of 0.1~1 mass parts.The flame-retardant polyurethane elastomer that the present invention is provided raw material based on carbon dioxide copolymer polyalcohol, PVC modified flame-retardant polyurethane elastomers are used, effectively improve burning drip phenomenon, simultaneously, decrease the addition of fire retardant, the combination property of PVC and TPU is combined, so that prepared modified flame-retardant polyurethane material has high fire-retardance effect and strong mechanical performance.
Description
Technical field
The invention belongs to fine polymer technical field, and in particular to a kind of flame-retardant polyurethane elastomer and its preparation side
Method.
Background technology
TPUE excellent performance, wear-resisting, oil resistant, high intensity and elongation at break etc., apply in recent years
It is more and more extensive.TPUE there is also some defects in itself simultaneously, such as：It is only 18 that limited oxygen index is relatively low
Left and right, belongs to combustible material, and for PAUR, its hydrolytic resistance is poor, is unsuitable to apply to make in high humility or water environment
With, and EU, its low intensity, wearability, scratch resistance difference type difference etc..TPUE of the prior art
As other most of macromolecular materials are similar, poor flame retardant properties, it is easy to which burning and burning molten drop phenomenon are serious, do not reach fire-retardant
It is required that, scope is used which has limited it, while the addition of substantial amounts of fire retardant, meets flame-retardancy requirements to a certain extent, while
Also result in the decline of other mechanical properties.With being stepped up to flame-retardancy requirements both at home and abroad, the simple fire-retardant effect of TPU materials
Really poor and fusing point is relatively low to cause to be particularly easy to drippage during burning that requirement cannot be met, therefore is also required to fire-retardant thermoplastic
Property polyurethane elastomer be modified treatment, improve its fire resistance, reduce the danger that fire occurs, protection people's life and
The safety of property.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of flame-retardant polyurethane elastomer and its preparation
Method, the flame-retardant polyurethane elastomer that the present invention is provided reduces the usage amount of fire retardant, and also with good fire-retardant
Performance and mechanical property.
The invention provides a kind of flame-retardant polyurethane elastomer, it is prepared from by the raw material including following mass parts：
The carbon dioxide copolymer polyalcohol of 100 mass parts；
The diisocyanate of 30~60 mass parts；
The Corvic of 10~50 mass parts；
The chain extender of 8~12 mass parts；
The catalyst of 0.01~0.5 mass parts；
The fire retardant of 10~40 mass parts；
The heat stabilizer of 0.1~1 mass parts；
The antioxidant of 0.1~1 mass parts.
Preferably, the carbon dioxide copolymer is with carbon dioxide as initiation material, in initiator, the effect of catalyst
Lower and epoxypropane copolymerization into；Molecular weight is 1000~8000, and hydroxy functionality is 2~6, intramolecular carbonate group
Mole fraction is 0.25~0.45.
Preferably, the diisocyanate is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and liquefaction two
One or more in methylenebis phenyl isocyanate.
Preferably, the chain extender is selected from one or more in ethylene glycol, BDO and diglycol.
Preferably, the catalyst be selected from stannous octoate, stannous iso caprylate and dibutyl tin laurate in one kind or
It is various.
Preferably, the heat stabilizer is selected from zinc stearate, barium stearate, organic tin and lead salt stabilizer
One or more.
Preferably, the fire retardant is halogen-free flame retardants, and the halogen-free flame retardants is selected from methyl-phosphoric acid dimethyl ester and/or double
Phenol A is double (diphenyl phosphoester).
Preferably, the antioxidant is selected from one or more in antioxidant 1010, antioxidant 264 and antioxidant BHT.
Present invention also offers a kind of above-mentioned flame-retardant polyurethane method for producing elastomers, comprise the following steps：
A) carbon dioxide copolymer polyalcohol, diisocyanate, catalyst and antioxidant are mixed, it is anti-at 60~80 DEG C
Answer 2~3 hours, obtain performed polymer；
B) by chain extender, heat stabilizer, fire retardant, Corvic and step A) after the performed polymer that obtains mixes
By vacuum outgas, solidification, curing, broken and granulation, flame-retardant polyurethane elastomer is obtained.
Preferably, isocyanate index is 1.05~1.2 in the flame-retardant polyurethane elastomer.
Compared with prior art, the invention provides a kind of flame-retardant polyurethane elastomer, by including following mass parts
Raw material is prepared from：The carbon dioxide copolymer polyalcohol of 100 mass parts；The diisocyanate of 30~60 mass parts；10~50
The Corvic of mass parts；The chain extender of 8~12 mass parts；The catalyst of 0.01~0.5 mass parts；10~40 mass parts
Fire retardant；The heat stabilizer of 0.1~1 mass parts；The antioxidant of 0.1~1 mass parts.The flame-retardant polyurethane that the present invention is provided
Elastomer raw material based on carbon dioxide copolymer polyalcohol, has used PVC modified flame-retardant polyurethane elastomers, effectively changes
It has been apt to burning drip phenomenon, meanwhile, the addition of fire retardant is decreased, the combination property of PVC and TPU is combined, so that
Obtaining prepared modified flame-retardant polyurethane material has high fire-retardance effect and strong mechanical performance.
Specific embodiment
The invention provides a kind of flame-retardant polyurethane elastomer, it is prepared from by the raw material including following mass parts：
The carbon dioxide copolymer polyalcohol of 100 mass parts；
The diisocyanate of 30~60 mass parts；
The Corvic of 10~50 mass parts；
The chain extender of 8~12 mass parts；
The catalyst of 0.01~0.5 mass parts；
The fire retardant of 10~40 mass parts；
The heat stabilizer of 0.1~1 mass parts；
The antioxidant of 0.1~1 mass parts.
The preparing raw material of the flame-retardant polyurethane elastomer that the present invention is provided includes the carbon dioxide copolymer of 100 mass parts
Polyalcohol.Preferably, in the present invention, the carbon dioxide copolymer is with carbon dioxide as initiation material, in catalyst
Effect it is lower with epoxypropane copolymerization into.The catalyst is preferably DMC catalysts (PBM).
Mn=1000~8000 of the carbon dioxide copolymer polyalcohol, preferably 2000~4000；Hydroxy functionality
It is 2~6, preferably 2~3；The mole fraction of intramolecular carbonate group is 0.25~0.45, preferably 0.30~0.40.
In the present invention, the carbon dioxide copolymer polyol molecule is contained within substantial amounts of carbonic acid ester bond and ehter bond, this
A little keys cause carbon dioxide copolymer polyalcohol when generating polyurethane is prepared, not only between its molecule, and in itself and amino
Stronger intramolecular and intermolecular hydrogen bonding is easily formed between formic acid esters, while having the mutually micro- isolating construction of soft and hard segments so that
Carbon dioxide copolymer polyol(poly)urethane elastomer has the characteristic of intensity high, hydrolysis, wearability, tensile strength of material
Height, properties are excellent, with wide market prospects.Also, the carbon dioxide copolymer polyalcohol is with carbon dioxide
Obtained in raw material, cost is respectively provided with significance after industrialization than less expensive to environmental protection, energy-saving and emission-reduction.
The preparing raw material of the flame-retardant polyurethane elastomer that the present invention is provided also two isocyanic acids including 30~60 mass parts
Ester, preferably 40~50 mass parts, more preferably 44~46 mass parts.The diisocyanate be selected from toluene di-isocyanate(TDI),
One or more in methyl diphenylene diisocyanate and liquefaction methyl diphenylene diisocyanate.
The preparing raw material of the flame-retardant polyurethane elastomer that the present invention the is provided also polyvinyl chloride including 10~50 mass parts
Resin, preferably 20~40 mass parts, more preferably 25~35 mass parts.
The preparing raw material of the flame-retardant polyurethane elastomer that the present invention the is provided also chain extender including 8~12 mass parts, it is excellent
Elect 9~11 mass parts, more preferably 9.5~10.5 mass parts as.The chain extender is selected from ethylene glycol, BDO and a contracting
One or more in diethylene glycol.
The also catalysis including 0.01~0.5 mass parts of the preparing raw material of the flame-retardant polyurethane elastomer that the present invention is provided
Agent, preferably 0.05~0.40 mass parts, more preferably 0.10~0.30 mass parts.The catalyst is selected from stannous octoate, different
One or more in stannous octoate and dibutyl tin laurate.
The preparing raw material of the flame-retardant polyurethane elastomer that the present invention the is provided also fire retardant including 10~40 mass parts, it is excellent
Elect 20~30 mass parts, more preferably 24~26 mass parts as.The fire retardant is preferably halogen-free flame retardants, the halogen-free flameproof
Agent is selected from methyl-phosphoric acid dimethyl ester and/or bisphenol-A is double (diphenyl phosphoester).
The preparing raw material of the flame-retardant polyurethane elastomer that the present invention the is provided also heat stabilizer including 0.1~1 mass parts,
Preferably 0.3~0.8 mass parts, more preferably 0.5~0.7 mass parts.The heat stabilizer is selected from zinc stearate, stearic acid
One or more in barium, organic tin and lead salt stabilizer.
The preparing raw material of the flame-retardant polyurethane elastomer that the present invention the is provided also antioxidant including 0.1~1 mass parts, it is excellent
Elect 0.3~0.8 mass parts, more preferably 0.5~0.7 mass parts as.The antioxidant is selected from antioxidant 1010, antioxidant 264
With one or more in antioxidant BHT.
Present invention also offers a kind of above-mentioned flame-retardant polyurethane method for producing elastomers, comprise the following steps：
A) carbon dioxide copolymer polyalcohol, isocyanates, catalyst and antioxidant are mixed, is reacted at 60~80 DEG C
2~3 hours, 50~60 DEG C are cooled to, obtain performed polymer；
B) by chain extender, heat stabilizer, fire retardant, Corvic and step A) after the performed polymer that obtains mixes
By vacuum outgas, solidification, curing, broken and granulation, flame-retardant polyurethane elastomer is obtained.
The present invention first mixes carbon dioxide copolymer polyalcohol, diisocyanate, catalyst and antioxidant.Wherein,
The carbon dioxide copolymer polyalcohol is by the carbon dioxide copolymer polyalcohol of vacuum dehydration.The vacuum dehydration is preferred
Carry out as follows：
By carbon dioxide copolymer polyalcohol under conditions of 120 DEG C vacuum dehydration 2~3 hours.
Carbon dioxide copolymer polyalcohol after vacuum dehydration is cooled to 50~60 DEG C, with diisocyanate, catalyst
With antioxidant mixing, reacted 2~3 hours at 60~80 DEG C, cool to 50~60 DEG C, obtain performed polymer component A.
Then, by chain extender, heat stabilizer, fire retardant, Corvic and above-mentioned performed polymer mix after by
Vacuum outgas, solidification, curing, broken and granulation, obtain flame-retardant polyurethane elastomer.
In the present invention, mix and be preferably high-speed stirred.It is anti-that the mixture that will be obtained after stirring carries out vacuum outgas
5~10min is answered, is subsequently poured into preheated mould, solidified and cured.Wherein, the temperature of the solidification is 60~100
DEG C, the time of solidification is 6~24 hours；The temperature of the curing is 60~120 DEG C, and the time of curing is 6~24 hours.Finally
Crushed and granulated, obtained flame-retardant polyurethane elastomer.Isocyanate index is in the flame-retardant polyurethane elastomer
1.05~1.2.
The flame retarding type thermoplastic polyurethane elastomer that the present invention is provided is heated temperature of initial decomposition compared to traditional poly- ammonia
Ester elastomer is relatively low, and the carbon dioxide produced by thermal decomposition is capable of the oxygen concentration on diluted material surface, and suppress material enters one
Step burning, so as to improve the fire resistance of material, compared with other fire proofings, the addition of fire retardant is also substantially reduced, into
This reduction.The flame retarding type thermoplastic polyurethane elastomer, combines the excellent properties of PVC and TPU, the mechanicalness high with TPU
Energy, anti-hydrolytic performance, Oil-resistant cold-resistant and the anti-flammability with PVC, and can effectively solve the problem that polyurethane elastomer burns
Drippage problem.
For a further understanding of the present invention, the flame-retardant polyurethane elastomer that is provided the present invention with reference to embodiment and
Its preparation method is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Take 100 parts of carbon dioxide copolymer polyalcohol, Guangdong Dazhi Environmental Protection Technology Co., Ltd., trade mark 3202h, plus
Enter in the glass reaction kettle with vacuum extractor, 120 DEG C vacuumize dehydration 2 hours, cool to 50 DEG C, add the two of fusing in advance
50 parts of methylenebis phenyl isocyanate, 0.02 part of stannous octoate, 0.2 part of antioxidant BHT, mixing speed 600r/min progressively adds
80 degree of heat is reacted 3 hours, obtains performed polymer component A, cools to 60 DEG C.100 parts of performed polymer component As are taken, then will be containing de- in advance
9.2 parts of the chain extender BDO of water, 20 parts of methyl-phosphoric acid dimethyl ester, 0.2 part of zinc stearate, the B component of 15 parts of polyvinyl chloride resin
In adding performed polymer component A, high-speed stirred vacuum outgas after reacting 5 minutes it is quick fall the preheated mould of people, in an oven 80
After solidifying 12h at DEG C, then 12h is cured at 100 DEG C, and crushed after room temperature places 24h, granulation is obtained novel flame-retardant thermoplasticity
Polyurethane elastomer particle.Performance test：Vertical combustion experiment is by fire-protection rating UL-94 tests, tensile strength and extension at break
Rate is tested by GB/T528-2009；Shao A hardness is tested by GB/T6031-1998.Mechanical property and combustibility are shown in Table 1.
Embodiment 2
Take 100 parts of carbon dioxide copolymer polyalcohol, Guangdong Dazhi Environmental Protection Technology Co., Ltd., trade mark 3202h, plus
Enter in the glass reaction kettle with vacuum extractor, 120 DEG C vacuumize dehydration 2 hours, cool to 60 DEG C, add the two of fusing in advance
55 parts of methylenebis phenyl isocyanate, 0.02 part of stannous octoate, 0.2 part of antioxidant BHT, mixing speed 600r/min progressively adds
80 degree of heat is reacted 3 hours, obtains performed polymer component A, cools to 60 DEG C.100 parts of performed polymer component As are taken, then will be containing de- in advance
9.7 parts of the chain extender BDO of water, 30 parts of methyl-phosphoric acid dimethyl ester, 0.2 part of zinc stearate, the B component of 20 parts of polyvinyl chloride resin
In adding performed polymer component A, high-speed stirred vacuum outgas after reacting 5 minutes it is quick fall the preheated mould of people, in an oven 80
After solidifying 12h at DEG C, then 12h is cured at 100 DEG C, and crushed after room temperature places 24h, granulation is obtained novel flame-retardant thermoplasticity
Polyurethane elastomer particle.Performance test：Vertical combustion experiment is by fire-protection rating UL-94 tests, tensile strength and extension at break
Rate is tested by GB/T528-2009；Shao A hardness is tested by GB/T6031-1998.Mechanical property and combustibility are shown in Table 1.
Embodiment 3
Take 100 parts of carbon dioxide copolymer polyalcohol, Guangdong Dazhi Environmental Protection Technology Co., Ltd., trade mark 3202h, plus
Enter in the glass reaction kettle with vacuum extractor, 120 DEG C vacuumize dehydration 2 hours, cool to 60 DEG C, add the two of fusing in advance
50 parts of methylenebis phenyl isocyanate, 0.02 part of stannous octoate, 0.2 part of antioxidant BHT, mixing speed 500r/min progressively adds
80 degree of heat is reacted 3 hours, obtains performed polymer component A, cools to 60 DEG C.100 parts of performed polymer component As are taken, then will be containing de- in advance
9.2 parts of the chain extender BDO of water, 30 parts of methyl-phosphoric acid dimethyl ester, 0.2 part of zinc stearate, the B component of 25 parts of polyvinyl chloride resin
In adding performed polymer component A, high-speed stirred vacuum outgas after reacting 5 minutes it is quick fall the preheated mould of people, in an oven 80
After solidifying 12h at DEG C, then 12h is cured at 100 DEG C, and crushed after room temperature places 24h, granulation is obtained novel flame-retardant thermoplasticity
Polyurethane elastomer particle.Performance test：Vertical combustion experiment is by fire-protection rating UL-94 tests, tensile strength and extension at break
Rate is tested by GB/T528-2009；Shao A hardness is tested by GB/T6031-1998.Mechanical property and combustibility are shown in Table 1.
Embodiment 4
Take 100 parts of carbon dioxide copolymer polyalcohol, Guangdong Dazhi Environmental Protection Technology Co., Ltd., trade mark 3202h, plus
Enter in the glass reaction kettle with vacuum extractor, 120 DEG C vacuumize dehydration 2 hours, cool to 60 DEG C, add the two of fusing in advance
50 parts of methylenebis phenyl isocyanate, 0.02 part of stannous octoate, 0.2 part of antioxidant BHT, mixing speed 500r/min progressively adds
80 degree of heat is reacted 3 hours, obtains performed polymer component A, cools to 60 DEG C.100 parts of performed polymer component As are taken, then will be containing de- in advance
9.2 parts of the chain extender BDO of water, 35 parts of methyl-phosphoric acid dimethyl ester, 0.2 part of zinc stearate, the B component of 30 parts of polyvinyl chloride resin
In adding performed polymer component A, high-speed stirred vacuum outgas after reacting 5 minutes it is quick fall the preheated mould of people, in an oven 80
After solidifying 18h at DEG C, then 12h is cured at 100 DEG C, and crushed after room temperature places 24h, granulation is obtained novel flame-retardant thermoplasticity
Polyurethane elastomer particle.Performance test：Vertical combustion experiment is by fire-protection rating UL-94 tests, tensile strength and extension at break
Rate is tested by GB/T528-2009；Shao A hardness is tested by GB/T6031-1998.Mechanical property and combustibility are shown in Table 1.
Embodiment 5
Take 100 parts of carbon dioxide copolymer polyalcohol, Guangdong Dazhi Environmental Protection Technology Co., Ltd., trade mark 3202h, plus
Enter in the glass reaction kettle with vacuum extractor, 120 DEG C vacuumize dehydration 2 hours, cool to 60 DEG C, add the two of fusing in advance
50 parts of methylenebis phenyl isocyanate, 0.02 part of stannous octoate, 0.2 part of antioxidant BHT, mixing speed 500r/min progressively adds
80 degree of heat is reacted 3 hours, obtains performed polymer component A, cools to 60 DEG C.100 parts of performed polymer component As are taken, then will be containing de- in advance
9.2 parts of the chain extender BDO of water, 30 parts of methyl-phosphoric acid dimethyl ester, 0.2 part of zinc stearate, the B component of 35 parts of polyvinyl chloride resin
In adding performed polymer component A, high-speed stirred vacuum outgas after reacting 5 minutes it is quick fall the preheated mould of people, in an oven 80
After solidifying 24h at DEG C, then 12h is cured at 100 DEG C, and crushed after room temperature places 24h, granulation is obtained novel flame-retardant thermoplasticity
Polyurethane elastomer particle.Performance test：Vertical combustion experiment is by fire-protection rating UL-94 tests, tensile strength and extension at break
Rate is tested by GB/T528-2009；Shao A hardness is tested by GB/T6031-1998.Mechanical property and combustibility are shown in Table 1.
Comparative example 1
Take 100 parts of carbon dioxide copolymer polyalcohol, Guangdong Dazhi Environmental Protection Technology Co., Ltd., trade mark 3202h, plus
Enter in the glass reaction kettle with vacuum extractor, 120 DEG C vacuumize dehydration 2 hours, cool to 60 DEG C, add the two of fusing in advance
50 parts of methylenebis phenyl isocyanate, 0.02 part of stannous octoate, 0.2 part of antioxidant BHT, mixing speed 600r/min progressively adds
80 degree of heat is reacted 3 hours, obtains performed polymer component A, cools to 60 DEG C.100 parts of performed polymer component As are taken, then will be containing de- in advance
9.2 parts of the chain extender BDO of water, 20 parts of methyl-phosphoric acid dimethyl ester, the B component of 0.2 part of zinc stearate add performed polymer A
In component, high-speed stirred vacuum outgas after reacting 5 minutes it is quick fall the preheated mould of people, solidify 12h at 80 DEG C in an oven
Afterwards, then at 100 DEG C 12h is cured, and is crushed after room temperature places 24h, granulation is obtained novel flame-retardant TPUE
Particle.Performance test：Vertical combustion experiment is tested by fire-protection rating UL-94, and tensile strength and elongation at break press GB/T528-
2009 tests；Shao A hardness is tested by GB/T6031-1998.Mechanical property and combustibility are shown in Table 1.
The embodiment 1~5 of table 1 and TPUE performance obtained by comparative example 1
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of flame-retardant polyurethane elastomer, it is characterised in that be prepared from by the raw material including following mass parts：
The carbon dioxide copolymer polyalcohol of 100 mass parts；
The diisocyanate of 30~60 mass parts；
The Corvic of 10~50 mass parts；
The chain extender of 8~12 mass parts；
The catalyst of 0.01~0.5 mass parts；
The fire retardant of 10~40 mass parts；
The heat stabilizer of 0.1~1 mass parts；
The antioxidant of 0.1~1 mass parts.
2. flame-retardant polyurethane elastomer according to claim 1, it is characterised in that the carbon dioxide copolymer be with
Carbon dioxide is initiation material, in the presence of initiator, catalyst with epoxypropane copolymerization into；Molecular weight be 1000~
8000, hydroxy functionality is 2~6, and the mole fraction of intramolecular carbonate group is 0.25~0.45.
3. flame-retardant polyurethane elastomer according to claim 1, it is characterised in that the diisocyanate is selected from toluene
One or more in diisocyanate, methyl diphenylene diisocyanate and liquefaction methyl diphenylene diisocyanate.
4. flame-retardant polyurethane elastomer according to claim 1, it is characterised in that the chain extender be selected from ethylene glycol,
One or more in BDO and diglycol.
5. flame-retardant polyurethane elastomer according to claim 1, it is characterised in that it is sub- that the catalyst is selected from octanoic acid
One or more in tin, stannous iso caprylate and dibutyl tin laurate.
6. flame-retardant polyurethane elastomer according to claim 1, it is characterised in that the heat stabilizer is selected from stearic acid
One or more in zinc, barium stearate, organic tin and lead salt stabilizer.
7. flame-retardant polyurethane elastomer according to claim 1, it is characterised in that the fire retardant is halogen-free flameproof
Agent, the halogen-free flame retardants is selected from methyl-phosphoric acid dimethyl ester and/or bisphenol-A is double (diphenyl phosphoester).
8. flame-retardant polyurethane elastomer according to claim 1, it is characterised in that the antioxidant is selected from antioxidant
1010th, one or more in antioxidant 264 and antioxidant BHT.
9. a kind of flame-retardant polyurethane method for producing elastomers as described in claim 1~8 any one, its feature exists
In comprising the following steps：
A) carbon dioxide copolymer polyalcohol, diisocyanate, catalyst and antioxidant are mixed, 2 is reacted at 60~80 DEG C
~3 hours, obtain performed polymer；
B) by chain extender, heat stabilizer, fire retardant, Corvic and step A) performed polymer that obtains mix after by
Vacuum outgas, solidification, curing, broken and granulation, obtain flame-retardant polyurethane elastomer.
10. preparation method according to claim 9, it is characterised in that isocyanic acid in the flame-retardant polyurethane elastomer
Ester index is 1.05~1.2.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251512A (en) * | 2018-09-17 | 2019-01-22 | 佛山市禅城区诺高环保科技有限公司 | A kind of long-acting weather-proof flame retarded rigid polyurethane foams |
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| CN113999368A (en) * | 2021-11-05 | 2022-02-01 | 中国科学院过程工程研究所 | Polyurethane polishing pad and preparation method thereof |
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| CN109251512A (en) * | 2018-09-17 | 2019-01-22 | 佛山市禅城区诺高环保科技有限公司 | A kind of long-acting weather-proof flame retarded rigid polyurethane foams |
| 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 |
| CN113801552A (en) * | 2021-10-18 | 2021-12-17 | 成都托展新材料股份有限公司 | Modified polyurea composition, preparation method and application thereof |
| CN113999368A (en) * | 2021-11-05 | 2022-02-01 | 中国科学院过程工程研究所 | Polyurethane polishing pad and preparation method thereof |
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Application publication date: 20170627 |