Background technology
Hard polyurethane foams is with polyol and isocyanic ester for raw material, through the foam materials of addition polymerization, foaming under the effect of such as catalyzer, whipping agent.This material has excellent physical and mechanical properties, electric property, acoustical behavior and chemical resistance, be in particular in that its thermal conductivity is low, density is little, intensity is high, water-absorbent is little, adiabatic, insulation, sound insulation, chemical stability be good, be hit after response rate high, be therefore widely used in the fields such as oil, chemical industry, transport, building.
At present, a lot of prior art is improved hard polyurethane foams, such as: CN101541850A discloses a kind of rigid urethane foam and preparation method thereof, this invention makes hydroxyl value be the rigid urethane foam that the polyvalent alcohol of 200-800mgKOH/g and polyisocyanate compound react preparation under the existence of amino modified siloxanes, catalyzer, whipping agent and suds-stabilizing agent; CN101544737A discloses a kind of rigid urethane foam and preparation method thereof, and this rigid urethane foam is generated by cyanate and thick polyether reactant.
Such as, but because polyurethane foam is a kind of inflammable substance, density is 30kg/m
3the oxygen index of polyurethane foam of left and right is only about 19, and its incendivity is close with cotton, runs into burning things which may cause a fire disaster or high bake very easily burns, and current many countries have also made laws the flame-retardant standard formulating material of construction.So the flame retardant resistance improving polyurethane foam is significant.
In order to meet the requirement to polyurethane foam flame retardant resistance, traditional method is that the method by adding a large amount of fire retardant reaches the effect improving flame retardant resistance.Conventional fire retardant is halogenated flame retardant, and more conventional halogen flame that is chloride, bromine is widely used.Such as CN101977995A discloses a kind of thermoplastic polyurethane preparaton, and this preparaton comprises halogenated flame and weisspiessglanz and talcum thereof.
But, a large amount of cigarettes can be produced when this kind of halogen flame that is chloride, bromine burns, and discharge poisonous and there is corrosive gas, if sucked the even death that easily causes suffocating, so some developed countries have started to prohibit the use halogen flame by human body.
By current situation, the task of top priority is the hard polyurethane foams inventing a kind of safety and environmental protection, make it, on the premium properties basis with hard polyurethane foams itself, to there is the flame retardant resistance of high-quality, also can not have high-risk-type as containing halogen flame hard polyurethane foams simultaneously.
Summary of the invention
In order to solve the defect of current hard polyurethane foams, producing a kind of hard polyurethane foams of safety and environmental protection, the invention provides a kind of expanded polystyrene veneer hard-foam polyurethane and preparation method thereof.
On the one hand, theme of the present invention is a kind of preparation method of expanded polystyrene veneer hard-foam polyurethane, comprising: mixed by raw material by proportioning, then pours in mould and foams, and obtains finally by slaking:
Wherein, described raw material and proportioning thereof comprise:
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, described polyisocyanates type is unrestricted.
According to a kind of preferred embodiment of the present invention first aspect, described polyisocyanates type, preferably, be selected from 4,4 '-'-diphenylmethane diisocyanate, diphenylmethanediisocyanate are correlated with modified product, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanates, poly methylene poly phenyl poly isocyanate or its relevant modified product.
Wherein, described diphenylmethanediisocyanate modified product of being correlated with is preferably Carbodiimide-Modified 4,4 diphenylmethanediisocyanates.
Wherein, described poly methylene poly phenyl poly isocyanate modified product of being correlated with is preferably p-nitrophenyl phenol block poly methylene poly phenyl poly isocyanate and para-chlorophenol closes poly methylene poly phenyl poly isocyanate.
Wherein, described polyisocyanates type, is more preferably, and the NCO% content of polyisocyanates is 18.0-36.0%.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, the type of described polyvalent alcohol is unrestricted.
According to a kind of preferred embodiment of the present invention first aspect, described polyhydric alcohol-type can select the conventional polyol for the manufacture of urethane, for material of construction hard polyurethane foams, preferably, the optional at least one in polyether glycol and polyester polyol of polyvalent alcohol; More preferably, described polyether glycol can be selected from the polyether polyol that the functionality formed for initiator with at least one of at least one in propylene glycol, ethylene glycol, glycerol, TriMethylolPropane(TMP), tetramethylolmethane, sucrose, sorbyl alcohol and quadrol and tolylene diamine is 2-6, hydroxyl value is 18-800; Most preferably, described polyester polyol is selected from least one and ethylene glycol, propylene glycol, glycerol, the TriMethylolPropane(TMP), 1 that backbone structure adopts hexanodioic acid and Tetra hydro Phthalic anhydride, 4-butyleneglycol, 1, the functionality that at least one polycondensation of 6 hexylene glycols, pentanediol is formed is 2-4, hydroxyl value is the polyester polyol of 50-500.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, the type of described catalyzer is unrestricted.
According to a kind of preferred embodiment of the present invention first aspect, described catalyzer, preferably, be selected from 1, 4-diazonium (2, 2, 2-cyclooctane), triethyl diamines (DABCO), N, N, N ', N ', N "-pentamethyl--diethyl triamine (PMDETA), N, N-dimethylcyclohexylamine (DMCHA), N, N-dimethyl benzylamine, N, N '-Tetramethyl Ethylene Diamine (TMEDA), Dimethylaminopropyl amine (DMAPA) AminZ, N, N-dimethylethanolamine (DMEA), 2, 4, 6-tri-(dimethylaminomethyl) phenol, N-ethylmorpholine (NEM), two N, N '-dimethyl amido ethyl ether, one or more of dibutyl tin dilaurate (DBTDL).
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, the type of described char-forming agent is unrestricted.
According to a kind of preferred embodiment of the present invention first aspect, described char-forming agent, preferably, is selected from one or more in starch, Mierocrystalline cellulose and derivative, sucrose, sorbyl alcohol, tetramethylolmethane and derivative, epoxy resin, resol.
Wherein, described derivatived cellulose, is preferably containing one or more in chain alkyl water-soluble cellulose derivative, sulphurous water soluble cellulose derivative and zwitter-ion group water-soluble cellulose derivative.
Wherein, described pentaerythritol derivative be preferably season penta tetrabromo, season penta tetramine and season penta Tetrahydroxyethyl ethylenediamine in one or more.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, described char forming catalyst is unrestricted.
According to a kind of preferred embodiment of the present invention first aspect, described char forming catalyst, preferably, one or more in primary ammonium phosphate, urea phosphate, ammonium polyphosphate, ammonium polyphosphate potassium, Potassium tripolyphosphate, melamine phosphate, phosphoric acid two trimeric cyanamide, melamine pyrophosphate, organophosphate, borate, ester and derivative, sulphonate and derivative are selected from.
Wherein, described sulfonate derivatives, is preferably, one or more in sulfamate, alkyl sulfonic ester ethylene glycol bisthioglycolate methanesulfonates and thionamic acid phenylester.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, the type of described one-tenth charcoal whipping agent is unrestricted.
According to a kind of preferred embodiment of the present invention first aspect, described one-tenth charcoal whipping agent, preferably, be selected from urea, biuret, aminoresin, urea-formaldehyde resin, melamine, melamine cyanurate, clorafin one or more.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, the type of described fire retardant is unrestricted.
According to a kind of preferred embodiment of the present invention first aspect, describedly state fire retardant types, can be the conventional flame retardants of this area for the manufacture of urethane, preferably, be selected from TECP, TCPP, TEP, DMMP, DEEP, melamine cyanurate, trimeric cyanamide, one or more of ammonium polyphosphate.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, described blowing agent type can be the Traditional blowing agents of this area for the manufacture of urethane.
According to a kind of preferred embodiment of the present invention first aspect, described blowing agent type, preferably, is selected from one or more in F11, HCFC-141b, HFC-245fa, HFC-365mfc, HFC-227ea.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, wherein, described foam stabilizer type can be the conventional foam stabilizer of this area for the manufacture of urethane, also can be the conventional oxidation inhibitor of this area for the manufacture of urethane.
According to a kind of preferred embodiment of the present invention first aspect, described foam stabilizer type, preferably, is selected from polydimethylsiloxane, silicon-oxygen-carbon is good for suds-stabilizing agent.
The preparation method of above-mentioned expanded polystyrene veneer hard-foam polyurethane provided by the invention, according to a kind of preferred embodiment of the present invention first aspect, wherein, preferably, raw material is by weight ratio:
Polyisocyanates 30-80 part, is more preferably 20-70 part, most preferably is 30-60 part;
Polyvalent alcohol 10-60 part, is more preferably 10-50 part, most preferably is 20-40 part;
Catalyzer 0.5-10 part, is more preferably 1-9 part, most preferably is 2-8 part;
Char-forming agent 0.5-10 part, is more preferably 1-9 part, most preferably is 3-8 part;
Char forming catalyst 0.5-5 part, is more preferably 1-4 part, most preferably is 1.5-3 part;
Become charcoal whipping agent 1-10 part, be more preferably 2-9 part, most preferably be 3-8 part;
Fire retardant 2-30 part, is more preferably 4-28 part, most preferably is 5-25 part;
Whipping agent 2-20 part, is more preferably 3-18 part, most preferably is 4-15 part;
Foam stabilizer 0.1-5 part, is more preferably 1-4 part, most preferably is 2-4 part.
Second aspect, theme of the present invention is a kind of expanded polystyrene veneer hard-foam polyurethane prepared according to first aspect content.
The third aspect, theme of the present invention is a kind of application of expanded polystyrene veneer hard-foam polyurethane in fire protection flame retarding prepared according to first aspect content.
Wherein, described expanded polystyrene veneer hard-foam polyurethane expanded by heating can form charring layer.
Wherein, described charring layer is cellular.
Expanded polystyrene veneer hard-foam polyurethane prepared by the present invention has excellent fire resistance, can expand and form cellular charring layer after being heated, and stops flame to spread further, effectively can reduce the flue dust in fire retardant and poison gas simultaneously.Flame retardant properties reaches B1 level, and smoke density is low, oxygen index more than 30.The fields such as building heat preservation, freezer, refrigerator car, military side storehouse, industrial pipeline can be widely used in.
Embodiment
The invention provides a kind of preparation method of expanded polystyrene veneer hard-foam polyurethane, comprising: by proportioning, various raw material is mixed, then pour in mould and foam, cut into sheet material finally by slaking.
Wherein, raw material comprises: polyisocyanates, polyvalent alcohol, catalyzer, char-forming agent, char forming catalyst, one-tenth charcoal whipping agent, fire retardant, whipping agent, foam stabilizer.
Wherein, raw material is by weight ratio: polyisocyanates 30-80 part, polyvalent alcohol 10-60 part, catalyzer 0.5-5 part, char-forming agent 0.5-10 part, char forming catalyst 0.5-5 part.Become charcoal whipping agent 1-10 part, fire retardant 2-30 part, whipping agent 2-20 part, foam stabilizer 0.1-5 part.
Below in conjunction with concrete case study on implementation, the preparation method of expanded polystyrene veneer hard-foam polyurethane is described in detail, to explain the present invention better.
embodiment 1
Proportioning raw materials is in Table 1-1:
The proportioning raw materials of table 1-1 expanded polystyrene veneer hard-foam polyurethane
Raw material |
Weight percentage (wt%) |
Polyisocyanates PM200 |
50 |
Polyvalent alcohol PS2352 |
25 |
Catalyst P C5+K15 |
2.5 |
Char-forming agent sorbyl alcohol |
3.0 |
Char forming catalyst ammonium polyphosphate |
1.5 |
Become charcoal whipping agent urea-formaldehyde resin |
3.0 |
Fire retardant TCPP+TEP |
10 |
Whipping agent 141B |
4.0 |
Foam stabilizer L6920 |
1.0 |
Foam pouring in mould after various raw material mixing according to the proportioning raw materials of table 1-1, obtained after slaking.The performance obtained is in Table 1-2:
The performance index of table 1-2 expanded polystyrene veneer hard-foam polyurethane
Performance index |
Unit |
Detected result |
Density |
kg/m
3 |
36.8 |
Thermal conductivity |
W/m·K |
0.022 |
Compressive strength |
MPa |
0.19 |
Dimensional stability |
% |
0.34 |
Oxygen index |
% |
30.5 |
Smoke density |
SDR |
25.44 |
Flame retardant rating |
/ |
B1 level |
Analysis can obtain: the density of the expanded polystyrene veneer hard-foam polyurethane of the present embodiment 1 is low, high insulating effect, and compressive strength is high, and smoke density is low, excellent fireproof performance, can reach B1 level.
embodiment 2
Proportioning raw materials is in Table 2-1:
The proportioning raw materials of table 2-1 expanded polystyrene veneer hard-foam polyurethane
Raw material |
Weight percentage (wt%) |
Polyisocyanates PM200 |
55 |
Polyvalent alcohol PS2352 |
20 |
Catalyst P C5+K15 |
2.0 |
Char-forming agent sorbyl alcohol |
2.5 |
Char forming catalyst ammonium polyphosphate |
1.8 |
Become charcoal whipping agent urea-formaldehyde resin |
3.0 |
Fire retardant TCPP+TEP |
10 |
Whipping agent 141B |
4.5 |
Foam stabilizer L6920 |
1.2 |
Foam pouring in mould after various raw material mixing according to the proportioning raw materials of table 2-1, obtained after slaking.The performance obtained is in Table 2-2:
The performance index of table 2-2 expanded polystyrene veneer hard-foam polyurethane
Performance index |
Unit |
Detected result |
Density |
kg/m
3 |
37.2 |
Thermal conductivity |
W/m·K |
0.020 |
Compressive strength |
MPa |
0.21 |
Dimensional stability |
% |
0.31 |
Oxygen index |
% |
31.0 |
Smoke density |
SDR |
23.44 |
Flame retardant rating |
/ |
B1 level |
Analysis can obtain: the density of the expanded polystyrene veneer hard-foam polyurethane of the present embodiment 2 is low, high insulating effect, and compressive strength is high, and smoke density is low, excellent fireproof performance, can reach B1 level.
embodiment 3
Proportioning raw materials is in Table 3-1:
The proportioning raw materials of table 3-1 expanded polystyrene veneer hard-foam polyurethane
Raw material |
Weight percentage (wt%) |
Polyisocyanates PM200 |
59 |
Polyvalent alcohol PS2352 |
20 |
Catalyst P C5+K15 |
2.5 |
Char-forming agent sorbyl alcohol |
1.5 |
Char forming catalyst ammonium polyphosphate |
1.5 |
Become charcoal whipping agent urea-formaldehyde resin |
2 |
Fire retardant TCPP+TEP |
8.0 |
Whipping agent 141B |
4.5 |
Foam stabilizer L6920 |
1.0 |
Foam pouring in mould after various raw material mixing according to the proportioning raw materials of table 3-1, obtained after slaking.The performance obtained is in Table 3-2:
The performance index of table 3-2 expanded polystyrene veneer hard-foam polyurethane
Performance index |
Unit |
Detected result |
Density |
kg/m
3 |
35.8 |
Thermal conductivity |
W/m·K |
0.022 |
Compressive strength |
MPa |
0.19 |
Dimensional stability |
% |
0.38 |
Oxygen index |
% |
31.5 |
Smoke density |
SDR |
24.44 |
Flame retardant rating |
/ |
B1 level |
Analysis can obtain: the density of the expanded polystyrene veneer hard-foam polyurethane of the present embodiment 3 is low, high insulating effect, and compressive strength is high, and smoke density is low, excellent fireproof performance, can reach B1 level.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.