CN109206618A - A kind of flame retardant polyurethane foamed material and preparation method thereof - Google Patents
A kind of flame retardant polyurethane foamed material and preparation method thereof Download PDFInfo
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- CN109206618A CN109206618A CN201810893335.9A CN201810893335A CN109206618A CN 109206618 A CN109206618 A CN 109206618A CN 201810893335 A CN201810893335 A CN 201810893335A CN 109206618 A CN109206618 A CN 109206618A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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Abstract
The invention discloses a kind of flame-retardant polyurethane foamed materials and preparation method thereof, compared with existing organic foam stabilizer, polyethers and silicon oil of low hydrogen content with diallyl sealing end carry out graft reaction, so that organic foam stabilizer has good emulsibility, increase the compatibility of polyurethane foam system, fire retardant is set to be more evenly distributed, flame retardant effect is more preferable.It has used the alkanol of long-chain to block in organic foam stabilizer system disclosed by the invention, has improved the compatibility of silicone oil and fire retardant, be distributed in fire retardant on the abscess wall of foam, to play the optimal effectiveness of fire retardant.
Description
Technical field
The invention belongs to polyurethanes technology fields, and in particular to a kind of flame retardant polyurethane foamed material and preparation method thereof.
Background technique
Foam stabiliser is technical point important in polyurethane preparation process, be related to polyurethane products percent opening,
Cell size and distribution, while the structure of foam stabiliser is dispersed with conclusive influence to fire retardant, to determine poly- ammonia
Feel and flame retardant property of the soft bubble of ester etc. apply index.Existing foam stabiliser, in polyurethane foam system, the abscess of foam
Slightly, flame retardant effect and uniformity want poor, are embodied in that polyurethane foam feel is coarse, there is big string hole, the fire-retardant effect of polyurethane foam
Fruit is bad, and the sponge flame retardant effect difference of different parts is big etc..
Summary of the invention
The object of the present invention is to provide a kind of flame retardant polyurethane foamed materials and preparation method thereof, for the soft bubble sea of flame retardant type
Continuous field can reduce the surface tension of each component in polyurethane foam system, increase the intersolubility of each component, control bubble
Size and uniformity, make fire retardant be more evenly distributed, good flame retardation effect.
The present invention adopts the following technical scheme:
A kind of preparation method of flame retardant polyurethane foamed material, comprising the following steps:
(1) using allyl alcohol, ethylene oxide and propylene oxide as raw material, in the presence of basic catalyst, reaction prepares allyl envelope
The oxidation copolymerization ether at end；
(2) it using the oxidation copolymerization ether of allyl capped as raw material, is reacted with metallic sodium, generates sodium alkoxide, then sodium alkoxide and alkyl halide
Hydrocarbon reaction generates alkyl-blocked allyl polyether；
(3) using hexamethyldisiloxane, octamethylcy-clotetrasiloxane, high containing hydrogen silicone oil as raw material, in the presence of acidic,
Reaction prepares silicon oil of low hydrogen content；
(4) using alkyl-blocked allyl polyether, silicon oil of low hydrogen content as raw material, in the presence of noble metal catalyst, reaction preparation
Composition 1；
(5) using allyl alcohol, ethylene oxide and propylene oxide as raw material, in the presence of basic catalyst, reaction prepares allyl envelope
The oxidation copolymerization ether at end；
(6) it using the oxidation copolymerization ether of allyl capped as raw material, is reacted with metallic sodium, generates sodium alkoxide, then sodium alkoxide and haloalkene
Propyl reaction generates the polyethers of diallyl sealing end；
(7) with hexamethyldisiloxane, octamethylcy-clotetrasiloxane and tetramethyldihydrogendisiloxane, exist in acidic catalyst
Under, reaction prepares the silicon oil of low hydrogen content that end group contains Si-H；
(8) polyethers of diallyl sealing end and end group contain the silicon oil of low hydrogen content of Si-H, in the presence of noble metal catalyst, reaction
Prepare composition 2；
(9) composition 1, composition 2 are mixed to get flame retardant type organic foam stabilizer；
(10) after polyethers, catalyst, water, fire retardant, flame retardant type organic foam stabilizer are mixed, isocyanation esterification is added
Object is closed, post curing is stirred, obtains flame retardant polyurethane foamed material.
Preferably, in the flame retardant type organic foam stabilizer, the mass percent of composition 2 is 10~20%.
In the present invention, in step (1), allyl alcohol, ethylene oxide, propylene oxide, basic catalyst mass ratio be (1~
10): (5~70): (10~60): (0.3~0.5)；In step (2), the oxidation copolymerization ether of allyl capped and rubbing for metallic sodium
, than being 1:1.2~2, the molar ratio of sodium alkoxide and halogenated alkane is 1:3 for you；In step (3), hexamethyldisiloxane, prestox ring
Tetrasiloxane, high containing hydrogen silicone oil molar ratio be 7: 30~120: 1；In step (4), alkyl-blocked allyl polyether contains with low
Si-H molar ratio in hydrogen silicone oil is 1:(1.1~2), the dosage of the noble metal catalyst is alkyl-blocked allyl polyether
With 5~20ppm of silicon oil of low hydrogen content gross mass；In step (5), allyl alcohol, ethylene oxide, propylene oxide, basic catalyst
Mass ratio is (1~10): (5~70): (10~60): (0.3~0.5)；In step (6), the oxidation copolymerization ether of allyl capped
It is 1:1.2~2 with the molar ratio of metallic sodium, the molar ratio of sodium alkoxide and halogenated allyl is 1:3；In step (7), two silicon of hexamethyl
The molar ratio of oxygen alkane, octamethylcy-clotetrasiloxane and tetramethyldihydrogendisiloxane is 1:(5~40): (1~5)；Step (8)
In, it is 1:(2.2~4 that the polyethers and end group of diallyl sealing end, which contain the Si-H molar ratio in the silicon oil of low hydrogen content of Si-H), institute
State noble metal catalyst dosage be diallyl sealing end polyethers and the end group silicon oil of low hydrogen content gross mass that contains Si-H 5~
20ppm。
In the present invention, in step (1), the basic catalyst is metal hydroxides；In step (2), halogenated alkane is
Brominated alkanes；In step (3), the hydrogen content of high containing hydrogen silicone oil is 1%-2%；The acidic catalyst includes highly acidic resin, dense
Sulfuric acid；In step (4), the noble metal catalyst is the compound of platinum, palladium or rhodium；In step (5), the basic catalyst is
Metal hydroxides；In step (6), halogenated allyl is bromo allyl；In step (7), the acidic catalyst includes strong
Acidic resins, the concentrated sulfuric acid；In step (8), the noble metal catalyst is the compound of platinum, palladium or rhodium.
In the present invention, in step (1), the temperature of reaction is 90 DEG C~130 DEG C, pressure is not more than 0.3 MPa, time 4
~8 hours；In step (2), the temperature that the oxidation copolymerization ether of allyl capped is reacted with metallic sodium is 80~120 DEG C, the time 2
~5 hours, the time that sodium alkoxide is reacted with halogenated alkane was 3~5 hours, and temperature is 80~120 DEG C；In step (3), the temperature of reaction
Degree is 30 DEG C~60 DEG C, and the time is 3~24 hours；In step (4), the temperature of reaction is 80 DEG C~120 DEG C, pressure is 0.5~
2atm, time are 1~5 hour；In step (5), the temperature of reaction is 90 DEG C~130 DEG C, pressure is not more than 0.3 MPa, time
It is 4~8 hours；In step (6), the temperature that the oxidation copolymerization ether of allyl capped is reacted with metallic sodium is 80~120 DEG C, the time
It is 2~5 hours, the time that sodium alkoxide is reacted with halogenated allyl is 3~5 hours, and temperature is 80~120 DEG C；In step (7), instead
The temperature answered is 30 DEG C~60 DEG C, and the time is 3~24 hours；In step (8), the temperature of reaction is 80 DEG C~120 DEG C, and pressure is
0.5~2atm, time are 1~5 hour.
In the present invention, in step (10), polyethers is glycerin polyether；Catalyst is tin catalyst, amine catalyst, preferred catalytic
In agent, the mass ratio of tin catalyst and amine catalyst is 1: 0.8~1.2；Isocyanate compound is TDI, and fire retardant is section's Lay
Grace OP1230.Polyethers, catalyst, water, fire retardant, organic foam stabilizer, isocyanate compound, solvent mass ratio
It is 100: 0.4~0.5: 3.5~4: 10~12: 0.7~0.8: 55~60: 8.5~9.5.
In the present invention, the chemical structural formula of the composition 1 is as follows:
Wherein, it is 5~30 that x, which is 40~120, y,；
The chemical structural formula of R is as follows:
Wherein, it is 0~70 that a, which is 5~70, b,；
The chemical structural formula of R` is as follows:
Wherein, c is 3~10；
The chemical structural formula of the composition 2 is as follows:
Wherein, it is 0~10 that d, which is 10~80, e,；
R’’Chemical structure it is as follows:
Wherein, it is 10~50 that f, which is 5~30, g,.
Flame retardant type organic foam stabilizer is preparing the application in flame retardant polyurethane foamed material；The flame retardant type is organic
Silicon foam stabilizer includes composition 1 and composition 2；
The chemical structural formula of the composition 1 is as follows:
Wherein, it is 5~30 that x, which is 40~120, y,；
The chemical structural formula of R is as follows:
Wherein, it is 0~70 that a, which is 5~70, b,；
The chemical structural formula of R` is as follows:
Wherein, c is 3~10；
The chemical structural formula of the composition 2 is as follows:
Wherein, it is 0~10 that d, which is 10~80, e,；
R’’Chemical structure it is as follows:
Wherein, it is 10~50 that f, which is 5~30, g,.
In the present invention, basic catalyst is metal hydroxides, such as potassium hydroxide, sodium hydroxide or bimetal hydroxide
Object；Halogenated alkane is butyl chloride；Halogenated allyl is allyl bromide, bromoallylene, extracts remaining halogenated alkane or haloalkene third after reaction out
Base filters to obtain product with diatomite or active carbon；Noble metal catalyst such as chloroplatinic acid (SpeierShi catalyst), platinum -1,3-
Divinyl -1,1,3- tetramethyl silicone complex (KarstedtShi catalyst).
The polyurethane foam of organic foam stabilizer production disclosed by the invention, uniform foam cell is fine and smooth, good hand touch effect
It is good；In polyurethane heat insulation material foaming system, make its polyurethane foam uniform foam cell, good flame retardation effect.
Organic foam stabilizer disclosed by the invention has block type polyethers compared with existing organic foam stabilizer
Modified silicon oil makes fire retardant be more evenly distributed, good flame retardation effect so that organic foam stabilizer has good emulsibility.
Detailed description of the invention
Fig. 1 is the polyurethane foam outside drawing of the present invention with the preparation of existing organic foam stabilizer.
Specific embodiment
Embodiment one
(1) allyl alcohol, ethylene oxide and propylene oxide are added in a kettle, under potassium hydroxide effect, controls reaction temperature
100 DEG C, reaction pressure no more than under conditions of 0.5 MPa, react 5 hours, cooling stops reaction, neutralized, filtering and extracting
The oxidation copolymerization ether of allyl capped is obtained after processing；Molecular weight is 2000, and EO molal quantity is 20, PO molal quantity in each molecule
It is 20；
(2) with step (1) prepare raw material, react 3 hours with metallic sodium in 100 DEG C, generation sodium alkoxide, then with allyl bromide, bromoallylene in
100 DEG C react 4 hours, it is evacuated, filter diallyl sealing end polyethers；
(3) hexamethyldisiloxane, octamethylcy-clotetrasiloxane, tetramethyldihydrogendisiloxane (high containing hydrogen silicone oil) are mixed,
The concentrated sulfuric acid is added, is reacted 18 hours under the conditions of temperature 50 C, obtains the silicon oil of low hydrogen content of linear chain structure；Molecular weight is 2000,
The molal quantity of dimethylsiloxane group is 25 in each molecule, trimethicone molal quantity 0.5, one hydrogen siloxane of dimethyl
Molal quantity be 1.5；
(4) silicon oil of low hydrogen content obtained by the resulting copolyether of step (2), step (3), SpeierShi catalyst are added to reaction kettle
In, under conditions of reaction temperature is 90 DEG C, reaction pressure is 1atm, react 5 hours；Obtain composition 2；
(5) allyl alcohol, ethylene oxide and propylene oxide are added in a kettle, under sodium hydroxide effect, controls reaction temperature
110 DEG C, reaction pressure no more than under conditions of 0.5 MPa, react 6 hours, cooling stops reaction, neutralized, filtering and extracting
The oxidation copolymerization ether of allyl capped is obtained after processing；Molecular weight is 3000, and EO molal quantity is 35, PO molal quantity in each molecule
It is 25；
(6) with step (5) prepare raw material, react 3 hours with metallic sodium in 100 DEG C, generation sodium alkoxide, then with butyl chloride 110
It is DEG C reaction 4 hours, evacuated, alkyl-blocked allyl polyether is obtained by filtration；
(7) it by hexamethyldisiloxane, octamethylcy-clotetrasiloxane, high containing hydrogen silicone oil tetramethyldihydrogendisiloxane, is added dense
Sulfuric acid reacts 15 hours under the conditions of 40 DEG C of temperature, obtains the silicon oil of low hydrogen content that end group contains Si-H；Molecular weight is 4000, often
The molal quantity of dimethylsiloxane group is 45 in one molecule, monomethyl siloxanes molal quantity 8.5；
(8) silicon oil of low hydrogen content obtained by the resulting alkyl-blocked allyl polyether of step (6), step (7), KarstedtShi are urged
Agent is added in reaction kettle, under conditions of reaction temperature is 80 DEG C~120 DEG C, reaction pressure is 0.5~2atm, reaction 3
~8 hours；After reaction, composition 1 is obtained；
Composition 2 is added into composition 1, is uniformly mixed to get the flame retardant type organic foam stabilizer, 2 mass hundred of composition is arrived
Score is 15%.
In step (1), allyl alcohol, ethylene oxide, propylene oxide, potassium hydroxide mass ratio be 5: 50: 30: 0.3；Step
(2) in, the molar ratio of the oxidation copolymerization ether of allyl capped and metallic sodium is 1:1.5, and the molar ratio of sodium alkoxide and allyl bromide, bromoallylene is
1:3；In step (3), hexamethyldisiloxane, octamethylcy-clotetrasiloxane, tetramethyldihydrogendisiloxane molar ratio be 7:
80:1；In step (4), the Si-H molar ratio in silicon oil of low hydrogen content obtained by the resulting copolyether of step (2), step (3) is 1:
1.3, the dosage of the noble metal catalyst is step (2) resulting copolyether, step (3) gained silicon oil of low hydrogen content gross mass
12ppm；In step (5), allyl alcohol, ethylene oxide, propylene oxide, sodium hydroxide mass ratio be 8: 45: 50: 0.4；Step
(6) in, the molar ratio of the oxidation copolymerization ether of allyl capped and metallic sodium is 1:1.8, and the molar ratio of sodium alkoxide and butyl chloride is 1:
3；In step (7), the molar ratio of hexamethyldisiloxane, octamethylcy-clotetrasiloxane and tetramethyldihydrogendisiloxane is 1: 28
:3；Si-H in step (8), in silicon oil of low hydrogen content obtained by the resulting alkyl-blocked allyl polyether of step (6), step (7)
Molar ratio is 1:3, and the dosage of the noble metal catalyst is that the polyethers of diallyl sealing end contains the low hydrogeneous of Si-H with end group
The 8ppm of silicone oil gross mass.
Embodiment two
(1) allyl alcohol, ethylene oxide and propylene oxide are added in a kettle, under sodium hydroxide effect, controls reaction temperature
110 DEG C, reaction pressure no more than under conditions of 0.5 MPa, react 6 hours, cooling stops reaction, neutralized, filtering and extracting
The oxidation copolymerization ether of allyl capped is obtained after processing；Molecular weight is 1000, and EO molal quantity is 15, PO molal quantity in each molecule
It is 6；
(2) with step (1) prepare raw material, react 4 hours with metallic sodium in 110 DEG C, generation sodium alkoxide, then with allyl bromide, bromoallylene in
120 DEG C react 3 hours, it is evacuated, filter diallyl sealing end polyethers；
(3) hexamethyldisiloxane, octamethylcy-clotetrasiloxane, tetramethyldihydrogendisiloxane are mixed, the concentrated sulfuric acid is added, in
It is reacted 15 hours under the conditions of 40 DEG C of temperature, obtains the containing hydrogen silicone oil of linear chain structure；Molecular weight is 3000, dimethyl in each molecule
The molal quantity of siloxane group is 39, trimethicone molal quantity 1, and the molal quantity of one hydrogen siloxane of dimethyl is 1；
(4) containing hydrogen silicone oil obtained by the resulting copolyether of step (2), step (3), KarstedtShi catalyst are added to reaction kettle
In, under conditions of reaction temperature is 100 DEG C, reaction pressure is 1.2atm, react 5 hours；Obtain composition 2；
(5) allyl alcohol, ethylene oxide and propylene oxide are added in a kettle, under potassium hydroxide effect, controls reaction temperature
110 DEG C, reaction pressure no more than under conditions of 0.5 MPa, react 8 hours, cooling stops reaction, neutralized, filtering and extracting
The oxidation copolymerization ether of allyl capped is obtained after processing；Molecular weight is 4000, and EO molal quantity is 50, PO molal quantity in each molecule
It is 31；
(6) with step (5) prepare raw material, react 3 hours with metallic sodium in 100 DEG C, generation sodium alkoxide, then with butyl chloride 110
It is DEG C reaction 4 hours, evacuated, alkyl-blocked allyl polyether is obtained by filtration；
(7) hexamethyldisiloxane, octamethylcy-clotetrasiloxane, high containing hydrogen silicone oil tetramethyldihydrogendisiloxane are mixed, is added
Enter the concentrated sulfuric acid, is reacted 19 hours under the conditions of temperature 50 C, obtain the containing hydrogen silicone oil of linear chain structure；Molecular weight is 3000, each
The molal quantity of dimethylsiloxane group is 35 in molecule, monomethyl siloxanes molal quantity 5；
(8) containing hydrogen silicone oil obtained by the resulting copolyether of step (6), step (7), SpeierShi catalyst are added to reaction kettle
In, under conditions of reaction temperature is 100 DEG C, reaction pressure is 1atm, react 6 hours；After reaction, composition 1 is obtained；
It is charged with composition 2, is uniformly mixed to get the flame retardant type organic foam stabilizer, 2 mass percent of composition is arrived
It is 15%.
In step (1), allyl alcohol, ethylene oxide, propylene oxide, potassium hydroxide mass ratio be 5: 50: 30: 0.3；Step
(2) in, the molar ratio of the oxidation copolymerization ether of allyl capped and metallic sodium is 1:1.5, and the molar ratio of sodium alkoxide and allyl bromide, bromoallylene is
1:3；In step (3), hexamethyldisiloxane, octamethylcy-clotetrasiloxane, tetramethyldihydrogendisiloxane molar ratio be 7:
80:1；In step (4), the Si-H molar ratio in silicon oil of low hydrogen content obtained by the resulting copolyether of step (2), step (3) is 1:
1.3, the dosage of the noble metal catalyst is step (2) resulting copolyether, step (3) gained silicon oil of low hydrogen content gross mass
12ppm；In step (5), allyl alcohol, ethylene oxide, propylene oxide, sodium hydroxide mass ratio be 8: 45: 50: 0.4；Step
(6) in, the molar ratio of the oxidation copolymerization ether of allyl capped and metallic sodium is 1:1.8, and the molar ratio of sodium alkoxide and butyl chloride is 1:
3；In step (7), the molar ratio of hexamethyldisiloxane, octamethylcy-clotetrasiloxane and tetramethyldihydrogendisiloxane is 1: 28
:3；Si-H in step (8), in silicon oil of low hydrogen content obtained by the resulting alkyl-blocked allyl polyether of step (6), step (7)
Molar ratio is 1:3, and the dosage of the noble metal catalyst is that the polyethers of diallyl sealing end contains the low hydrogeneous of Si-H with end group
The 8ppm of silicone oil gross mass.
Embodiment three
It is (art-recognized relatively good at present with existing foaming system using the flame retardant type organic foam stabilizer of embodiment
Import silicone oil) it compares, polyurethane foam is prepared respectively (in addition to the stabilizer of embodiment one, embodiment two, remaining raw material city
Purchase), specific preparation process is as follows:
200 grams of glycerin polyethers of foamed polyether, 3110,22 grams of fire retardant OP1230,0.46 gram of tin catalyst are added in foaming rotor
T9,0.44 donaxine catalyst A33,7.8 grams of water, 18 grams of methylene chloride and 1.5 grams of foam stabiliser, are then stirred with high-speed mixer
It mixes 2 minutes, material is uniformly mixed, 113 grams of TDI are then added, high-speed stirred 8 seconds, pour into container immediately after, to ripe
Change 2 days, incision sees abscess, surveys air penetrability and flame retardant property.
Attached drawing 1 is the polyurethane foam outside drawing of the present invention with the preparation of existing organic foam stabilizer, and B is existing import
The sponge of silicone oil foaming, 1 and 2 be respectively the sponge product of embodiment one and two；From the foam structure of foam, relative to existing
There is product, the foam cell that the present invention makes is very fine and smooth, uniform, and it is few to go here and there hole, especially flame retardant type silicon foams
The fine and smooth degree and excellent in uniformity of stabilizer abscess.
Organic foam stabilizer and relatively good import silicone oil domestic at present with the formula preparation in embodiment
Using Comparative result, performance is shown in Table 1, and as can be seen from the table, sample flame retardant effect in embodiment is well very than imported product
It is more, illustrate that fire retardant is more evenly distributed, has maximumlly played the left and right of fire retardant；In addition the sample in case study on implementation is being stretched
In long rate and tearing strength advantageously than imported product, illustrate abscess more evenly, defect is few；According to existing foaming system
(organic foam stabilizer and the preparation method and application thereof) compares, gas permeability 488；Only use composition 1, obtained gas permeability
It is 528.
The organic foam stabilizer of 1 embodiment of table and existing import silicone oil application performance
Claims (8)
1. a kind of preparation method of flame retardant polyurethane foamed material, which comprises the following steps:
(1) using allyl alcohol, ethylene oxide and propylene oxide as raw material, in the presence of basic catalyst, reaction prepares allyl envelope
The oxidation copolymerization ether at end；
(2) it using the oxidation copolymerization ether of allyl capped as raw material, is reacted with metallic sodium, generates sodium alkoxide, then sodium alkoxide and alkyl halide
Hydrocarbon reaction generates alkyl-blocked allyl polyether；
(3) using hexamethyldisiloxane, octamethylcy-clotetrasiloxane, high containing hydrogen silicone oil as raw material, in the presence of acidic,
Reaction prepares silicon oil of low hydrogen content；
(4) using alkyl-blocked allyl polyether, silicon oil of low hydrogen content as raw material, in the presence of noble metal catalyst, reaction preparation
Composition 1；
(5) using allyl alcohol, ethylene oxide and propylene oxide as raw material, in the presence of basic catalyst, reaction prepares allyl envelope
The oxidation copolymerization ether at end；
(6) it using the oxidation copolymerization ether of allyl capped as raw material, is reacted with metallic sodium, generates sodium alkoxide, then sodium alkoxide and haloalkene
Propyl reaction generates the polyethers of diallyl sealing end；
(7) with hexamethyldisiloxane, octamethylcy-clotetrasiloxane and tetramethyldihydrogendisiloxane, exist in acidic catalyst
Under, reaction prepares the silicon oil of low hydrogen content that end group contains Si-H；
(8) polyethers of diallyl sealing end and end group contain the silicon oil of low hydrogen content of Si-H, in the presence of noble metal catalyst, reaction
Prepare composition 2；
(9) composition 1, composition 2 are mixed to get flame retardant type organic foam stabilizer；
(10) after polyethers, catalyst, water, fire retardant, flame retardant type organic foam stabilizer and solvent are mixed, isocyanide is added
Ester compound stirs post curing, obtains flame retardant polyurethane foamed material.
2. the preparation method of flame retardant polyurethane foamed material according to claim 1, which is characterized in that the flame retardant type is organic
In silicon foam stabilizer, the mass percent of composition 2 is 10~20%.
3. the preparation method of flame retardant polyurethane foamed material according to claim 1, it is characterised in that: in step (1), alkene
Propyl alcohol, ethylene oxide, propylene oxide, basic catalyst mass ratio be (1~10): (5~70): (10~60): (0.3~
0.5)；In step (2), the oxidation copolymerization ether of allyl capped and the molar ratio of metallic sodium are 1:1.2~2, sodium alkoxide and alkyl halide
The molar ratio of hydrocarbon is 1:3；In step (3), the molar ratio of hexamethyldisiloxane, octamethylcy-clotetrasiloxane, high containing hydrogen silicone oil
It is 7: 30~120: 1；In step (4), the Si-H molar ratio in alkyl-blocked allyl polyether and silicon oil of low hydrogen content is 1:
(1.1~2), the dosage of the noble metal catalyst be alkyl-blocked allyl polyether and silicon oil of low hydrogen content gross mass 5~
20ppm；In step (5), allyl alcohol, ethylene oxide, propylene oxide, basic catalyst mass ratio be (1~10): (5~70):
(10~60): (0.3~0.5)；In step (6), the molar ratio of the oxidation copolymerization ether of allyl capped and metallic sodium be 1:1.2~
2, the molar ratio of sodium alkoxide and halogenated allyl is 1:3；In step (7), hexamethyldisiloxane, octamethylcy-clotetrasiloxane and four
The molar ratio of methyl dihydro disiloxane is 1:(5~40): (1~5)；In step (8), the polyethers of diallyl sealing end and end
It is 1:(2.2~4 that base, which contains the Si-H molar ratio in the silicon oil of low hydrogen content of Si-H), the dosage of the noble metal catalyst is diene
The polyethers and end group of propyl sealing end contain 5~20ppm of the silicon oil of low hydrogen content gross mass of Si-H.
4. the preparation method of flame retardant polyurethane foamed material according to claim 1, it is characterised in that: described in step (1)
Basic catalyst is metal hydroxides；In step (2), halogenated alkane is brominated alkanes；In step (3), high containing hydrogen silicone oil
Hydrogen content is 1%-2%；The acidic catalyst includes highly acidic resin, the concentrated sulfuric acid；In step (4), the noble metal catalyst
For the compound of platinum, palladium or rhodium；In step (5), the basic catalyst is metal hydroxides；In step (6), haloalkene third
Base is bromo allyl；In step (7), the acidic catalyst includes highly acidic resin, the concentrated sulfuric acid；It is described expensive in step (8)
Metallic catalyst is the compound of platinum, palladium or rhodium.
5. the preparation method of flame retardant polyurethane foamed material according to claim 1, it is characterised in that: in step (1), instead
The temperature answered is 90 DEG C~130 DEG C, pressure is not more than 0.3 MPa, the time is 4~8 hours；In step (2), allyl capped
The temperature that oxidation copolymerization ether is reacted with metallic sodium be 80~120 DEG C, the time be 2~5 hours, sodium alkoxide reacted with halogenated alkane when
Between be 3~5 hours, temperature be 80~120 DEG C；In step (3), the temperature of reaction is 30 DEG C~60 DEG C, and the time is 3~24 small
When；In step (4), the temperature of reaction is 80 DEG C~120 DEG C, and pressure is 0.5~2atm, and the time is 1~5 hour；Step (5)
In, the temperature of reaction is 90 DEG C~130 DEG C, pressure is not more than 0.3 MPa, the time is 4~8 hours；In step (6), allyl
The temperature that the oxidation copolymerization ether of sealing end is reacted with metallic sodium is 80~120 DEG C, and the time is 2~5 hours, sodium alkoxide and halogenated allyl
The time of reaction is 3~5 hours, and temperature is 80~120 DEG C；In step (7), the temperature of reaction is 30 DEG C~60 DEG C, the time 3
~24 hours；In step (8), the temperature of reaction is 80 DEG C~120 DEG C, and pressure is 0.5~2atm, and the time is 1~5 hour.
6. the preparation method of flame retardant polyurethane foamed material according to claim 1, it is characterised in that: in step (10), gather
Ether is glycerin polyether；Catalyst is tin catalyst, amine catalyst；Isocyanate compound is TDI；Solvent is methylene chloride.
7. the preparation method of flame retardant polyurethane foamed material according to claim 1, it is characterised in that: the change of the composition 1
It is as follows to learn structural formula:
Wherein, it is 5~30 that x, which is 40~120, y,；
The chemical structural formula of R is as follows:
Wherein, it is 0~70 that a, which is 5~70, b,；
The chemical structural formula of R` is as follows:
Wherein, c is 3~10；
The chemical structural formula of the composition 2 is as follows:
Wherein, it is 0~10 that d, which is 10~80, e,；
R’’Chemical structure it is as follows:
Wherein, it is 10~50 that f, which is 5~30, g,.
8. flame retardant type organic foam stabilizer is preparing the application in flame retardant polyurethane foamed material；The flame retardant type organosilicon
Foam stabiliser includes composition 1 and composition 2；
The chemical structural formula of the composition 1 is as follows:
Wherein, it is 5~30 that x, which is 40~120, y,；
The chemical structural formula of R is as follows:
Wherein, it is 0~70 that a, which is 5~70, b,；
The chemical structural formula of R` is as follows:
Wherein, c is 3~10；
The chemical structural formula of the composition 2 is as follows:
Wherein, it is 0~10 that d, which is 10~80, e,；
R’’Chemical structure it is as follows:
Wherein, it is 10~50 that f, which is 5~30, g,.
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| CN113845687A (en) * | 2021-11-03 | 2021-12-28 | 四川大学 | Efficient flame-retardant smoke-inhibiting low-density organic silicon foam material and preparation method thereof |
| CN113845687B (en) * | 2021-11-03 | 2022-05-20 | 四川大学 | Efficient flame-retardant smoke-inhibiting low-density organic silicon foam material and preparation method thereof |
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