CN107892739B - A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof - Google Patents
A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof Download PDFInfo
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- CN107892739B CN107892739B CN201711327640.3A CN201711327640A CN107892739B CN 107892739 B CN107892739 B CN 107892739B CN 201711327640 A CN201711327640 A CN 201711327640A CN 107892739 B CN107892739 B CN 107892739B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- 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
- C08G18/61—Polysiloxanes
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- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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Abstract
The invention discloses a kind of flame retarded rigid polyurethane foams plastics and preparation method thereof, it is made by raw material, the raw material includes following components in parts by weight: 100 part of first polyether polyol, 5-50 parts of flame retardant polyether polyols, 0.01-5 parts of foaming agents, 0.01-5 parts of foam stabilisers, the first catalyst of 0.02-2.5 part and fire-retardant polyisocyanates, and the molar ratio of fire-retardant polyisocyanates and " the pure and mild flame retardant polyether polyol of the first polyether polyols " total amount is 1.02:1-3:1.The flame retarded rigid foams plastics heat resistance is good, compressive strength is high, and has good flame retardant property；Its raw material sources used is abundant, inexpensive simultaneously, and preparation process applicability is wide, easy to operate, therefore has broad application prospects.
Description
Technical field
The present invention relates to polymer thermal insulative field of material technology, and in particular to a kind of flame retarded rigid polyurethane foams plastics and
Preparation method.
Background technique
Since rigid polyurethane foam has excellent thermal insulation property and good mechanical property, it is widely used in
Skyscraper Material Field.However, fire of high-rise building takes place frequently and brings serious loss to the country and people in recent years, keep the temperature
The anti-flammability of material directly affects whether skyscraper has flame retardant property.Therefore, flame-retardant hard polyurethane foam material is developed
Material is of great significance.
Currently, mainly having addition type and two kinds of response type to the flame resistant method of rigid polyurethane foam, with addition type
Flame retarded rigid polyurethane foams material is compared, and response type High-flame-retardanthard hard polyurethane foam has more preferably compatibility, more
High mechanical property and the advantages that do not migrate, and the less cigarette with corrosivity and toxicity is discharged in burning.About anti-
The fire retardant in type High-flame-retardanthard hard polyurethane foam is answered, is divided into halogen system, phosphorus system, halogen-phosphorus system, nitrogen by element species
System, silicon systems, high purity alumina-magnesia etc., wherein halogenated flame retardant discharges the hydrogen halides being largely harmful to the human body during polymer combustion.
So far, the modified mode of reaction-type flame-retarding is carried out with modified polyether polylol to rigid polyurethane foam
Based on.103467732 A of Chinese patent literature CN discloses a kind of synthetic method of flame retardant polyether polyol, in this method, hair
Bright people prepares initiator using low relative molecular weight polyethers and phosphorus-containing compound, then anti-with oxyalkylene under the action of catalyst
Phosphorous polyether polyol should be made, but do not refer to that the phosphorous polyether polyol prepares the flame retardant property of material in text.In China
Disclose in 103833947 A of patent of invention CN: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is to more
First alcohol progress is flame-retardant modified, when flame-proof polyol accounts for the 80% of polyether polyol, the limit oxygen of modified rigid polyurethane foam
Index (LOI) is promoted to 23.9% by 19.2%.But due to the higher cost of DOPO, it is limited in hard polyurethane foams
Application in plastic applications.Chinese patent literature CN105199096 A discloses a kind of preparation method of flame retardant polyether polyol,
Its raw material is complicated, preparation process is cumbersome, and raw materials used formaldehyde is the substance being harmful to the human body, and is unsuitable for industrialization production.Cause
This, explores the flame retardant property that polyurethane foam can be improved and has suitable for the flame retardant polyether polyol of industrialization production important
Theory significance and application value.In addition, polyisocyanates is also to be highly combustible in the raw material of polyurethane as organic matter.Resistance
Combustion modified polyisocyanate mainly by halogen, phosphonium flame retardant by chemical bonding by way of introduce polyisocyanates point
It is realized in minor structure, however halogenated flame retardant discharges a large amount of toxic and corrosive hydrogen halides during polymer combustion.
Only consider to do polyether polyol flame-retardant modified, the flame retardant property of rigid polyurethane foam is improved than relatively limited, still
It is to be improved.Therefore exploring the New Rigid polyurethane foam plastics that new method of modifying acquisition flame retardant property significantly improves has
Important theory significance and application value.
Summary of the invention
The present invention is practical, and the technical problem to be solved is that in order to overcome rigid polyurethane foam in the prior art
Flame retardant property it is low and it contains reactive flame retardant-halogenated flame retardant and discharges the halogen that is largely harmful to the human body in burning
The defects of changing hydrogen provides a kind of flame retarded rigid polyurethane foams plastics and preparation method thereof.The flame retarded rigid foams plastics
Heat resistance is good, compressive strength is high, limit oxygen index is higher, smoke density is lower, and has (the UL-94 resistance of good flame retardant property
Grade is fired up to V-0 grades)；Meanwhile raw material sources of the present invention are abundant, inexpensive, preparation process applicability is wide, operates
Simply, it is suitable for industrialization production, therefore has broad application prospects.
The present invention is to solve above-mentioned technical problem by following technical proposals:
The present invention provides a kind of flame retarded rigid polyurethane foams plastics, are made by raw material, and the raw material includes following
The component of parts by weight: 100 part of first polyether polyol, 5-50 parts of flame retardant polyether polyols, 0.01-5 parts of foaming agents, 0.01-5 parts
Foam stabiliser, the first catalyst of 0.02-2.5 part and fire-retardant polyisocyanates, the fire-retardant polyisocyanates and " described the
The molar ratio of the pure and mild flame retardant polyether polyol of one polyether polyols " total amount is 1.02:1-3:1；
The flame retardant polyether polyol is made by raw material, and raw material includes following components in parts by weight: 10 parts of melamines,
The second polyether polyol of 25-60 part, 18-36 parts of phosphorus oxychloride and 200-250 parts of solvents；
The fire-retardant polyisocyanates is made by raw material, and raw material includes the component of following parts by weight: 0.5-2 parts of hyperbranched polies
Siloxanes, 30 parts of polyisocyanates and 300-600 parts of n,N-Dimethylformamide；
The hyperbranched polyorganosiloxane is made by raw material, and raw material includes such as following components: water, the second catalyst, N, N- bis-
Methylformamide, amino-trialkoxy silane, phenyl trialkoxysilane, end-capping reagent and polyisocyanates, it is the water, described
Second catalyst, the n,N-Dimethylformamide, the amino-trialkoxy silane, the phenyl trialkoxysilane, institute
The molar ratio for stating end-capping reagent and the polyisocyanates is 10:(0.02-0.04): (30-60): 2:(1-4): (10-15): 30.
In the present invention, first polyether polyol or second polyether polyol can be more for the polyethers of this field routine
One of first alcohol, preferably polyethylene oxide polyol, polyoxypropylene polyol and polytetrahydrofuran ethoxylated polyhydric alcohol or
It is a variety of.
In the present invention, the hydroxyl value of first polyether polyol is preferably 270-520mg KOH/g, more preferably for
395mg KOH/g.The equal relative molecular weight of number of first polyether polyol can be conventional for this field, preferably 300-800,
It is more preferably 550.
In the present invention, the hydroxyl value of second polyether polyol is preferably 450-550mg KOH/g, more preferably for
500mg KOH/g.The equal relative molecular weight of number of second polyether polyol is preferably 300-400, is more preferably 350.
In the present invention, the dosage of second polyether polyol can be conventional for this field, preferably 29.3 parts or
40.3 parts.
In the present invention, the dosage of the flame retardant polyether polyol is preferably 25 parts.
In the present invention, the dosage of the foaming agent is preferably 2.5 parts.
In the present invention, the foaming agent can be the foaming agent of this field routine, preferably a fluorine dichloroethanes (HCFC-
141b), one of pentane, pentamethylene and water or a variety of.
In the present invention, the dosage of the foam stabiliser is preferably 2.5 parts.
In the present invention, institute's foam stabiliser can be the foam stabiliser of this field routine, preferably foam stabiliser
One of B8870, foam stabiliser L6950 and foam stabiliser AK8805 or a variety of.
In the present invention, the dosage of first catalyst is preferably 1.2 parts.
In the present invention, first catalyst can be the catalyst of this field routine, preferably triethylenediamine, two
One of dibutyl tin laurate, stannous octoate, triethylamine, triethanolamine and dibutyltin diacetate are a variety of.
In the present invention, the fire-retardant polyisocyanates and " the pure and mild flame retardant polyether polyol of the first polyether polyols "
The molar ratio of total amount is preferably 2:1 or 1.5:1.
In the present invention, the dosage of the phosphorus oxychloride is preferably 20.2 parts or 30.2 parts.
In the present invention, the solvent can be the solvent of this field routine, preferably one in toluene, dimethylbenzene and acetonitrile
Kind is a variety of.
In the present invention, the dosage of the hyperbranched polyorganosiloxane is preferably 0.75 part.
In the present invention, the hyperbranched polyorganosiloxane is through blocking the hyperbranched polyorganosiloxane containing amino and phenyl.It is described
The degree of branching of hyperbranched polyorganosiloxane can be conventional for this field, preferably 0.63-0.75 is more preferably 0.68.It is described super
The equal relative molecular weight of the weight of branched polysiloxane can be conventional for this field, and preferably 8000-12000 is more preferably 9000.
In the present invention, the water can be the water of this field routine, preferably distilled water.
In the present invention, second catalyst can be this field routine catalyst, preferably hydrochloric acid, sulfuric acid, to first
One of benzene sulfonic acid, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, sodium hydroxide and potassium hydroxide are a variety of.
In the present invention, the amino-trialkoxy silane can be the silicon containing amino and tri-alkoxy of this field routine
Alkane, preferably 3- TSL 8330 and/or gamma-aminopropyl-triethoxy-silane.
In the present invention, the dosage of the phenyl trialkoxysilane is preferably 3.6 parts.
In the present invention, the phenyl trialkoxysilane can be the silane containing phenyl and tri-alkoxy of this field routine,
Preferably phenyltrimethoxysila,e and/or phenyl triethoxysilane.
In the present invention, the end-capping reagent can be the end-capping reagent of this field routine, preferably hexamethyldisiloxane, front three
One of base chlorosilane, tri-phenyl chloride and chlorotriethyl silane are a variety of.
In the present invention, the flame retardant polyether polyol can be made by conventional method in that art, preferably, by following
Step is made:
(1) under an inert atmosphere, by the melamine, second polyether polyol, the phosphorus oxychloride with it is described
The mixture of solvent heats, insulation reaction；
(2) it is heated to reflux to hydrogen chloride gas and discharges, obtain the flame retardant polyether polyol after cooling.
In step (1), the inert atmosphere can be the inert atmosphere of this field routine, such as helium, neon or nitrogen, compared with
It goodly is nitrogen.
In step (1), the temperature after heating can be conventional for this field, and preferably 50-70 DEG C, be more preferably 60 DEG C.
In step (1), the time of the insulation reaction can be conventional for this field, preferably 1-3h.
In step (2), the temperature after cooling can be conventional for this field, preferably room temperature.The room temperature can be this
Field is conventional, and generally 10-30 DEG C.
In the present invention, the fire-retardant polyisocyanates can be made by conventional method in that art, preferably, passing through following steps
It is rapid to be made:
(1) under agitation, the amino-trialkoxy silane and the phenyl trialkoxysilane are added dropwise to molten
It in liquid A, heats up, reaction obtains solution B；The solution A is the water, second catalyst and the N, N- dimethyl methyl
The mixed solution of amide；
(2) end-capping reagent is added in the solution B, reacts, obtains the hyperbranched polyorganosiloxane；
(3) it is stirring under inert atmosphere conditions, the hyperbranched polyorganosiloxane made from step (2) is being added dropwise to
In the polyisocyanates and the mixed solution of the n,N-Dimethylformamide, after first set reaction, then the carry out that heats up
Secondary response is up to the fire-retardant polyisocyanates.
In step (1), the solution A can be made by conventional method in that art, be preferably made in the steps below: lazy
Under property atmosphere, " mixture of the water and second catalyst " is mixed with the n,N-Dimethylformamide to obtain the final product.Its
In, the inert atmosphere can be conventional for this field, such as helium, neon and nitrogen, preferably nitrogen.
In step (1), the condition of the reaction can be the condition of this field routine, preferably 50-60 DEG C reaction 8-
10h is more preferably 55~58 DEG C of reaction 9h.
In step (2), the time of the reaction can be conventional for this field, and preferably 3-6h is more preferably 4h.
In step (3), the temperature of the first set reaction can be conventional for this field, preferably 0-25 DEG C, more preferably for
13℃。
In step (3), the time of the first set reaction can be conventional for this field, and preferably 3-5h is more preferably 4h.
In step (3), the temperature of second secondary response can be conventional for this field, preferably 50-70 DEG C, more preferably for
60℃。
In step (3), the time of second secondary response can be conventional for this field, and preferably 4-6h is more preferably 5h.
The present invention also provides the preparation methods of the flame retarded rigid polyurethane foams plastics described in one kind comprising Xia Shubu
It is rapid:
(1) by first polyether polyol, the flame retardant polyether polyol, the foaming agent, the foam stabiliser
It is stirred with first catalyst；
(2) the fire-retardant polyisocyanates, mixing is added；
(3) it injects in mold and foams, cure up to flame retarded rigid polyurethane foams plastics.
In step (1), the mixed condition can be the condition of this field routine.The mixed temperature is preferably
20-60 DEG C, be more preferably 45 DEG C.
In step (2), the mixed condition can be the condition of this field routine, generally mix by stirring.
In step (3), the temperature of the mold can be conventional for this field, preferably 15-70 DEG C, more preferably for 55 DEG C or
60 DEG C of person.
In step (3), the temperature of the curing can be conventional for this field, and preferably 20-100 DEG C, be more preferably 75
DEG C or 80 DEG C.
It will be appreciated that " first " of the invention, " second " without practical significance, only distinguish the substance in different step, or
Identical term.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
The heat resistance of flame retarded rigid foams plastics of the invention is good, compressive strength is high, limit oxygen index is higher, smoke density
It is lower, and there are good flame retardant property (UL-94 flame retardant rating is up to V-0 grades).Fire-retardant polyisocyanates of the invention is being made
Catalytic action can be played during standby hard polyurethane foam, reduce the use of micromolecule catalyst and improves poly- ammonia
The flame retardant property of ester rigid foam；Meanwhile halogenated flame retardant is not contained, a large amount of toxic and corrosivity will not be discharged in burning
Hydrogen halides, protect environment, have a extensive future.
Meanwhile raw material sources of the present invention are abundant, inexpensive, preparation process applicability is wide, easy to operate, is suitable for
Industrialization production, therefore have broad application prospects.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Embodiment 1
1, the preparation of flame retardant polyether polyol
It is 300 by 10.0g melamine, the equal relative molecular weight of 60.0g number by quality under the conditions of nitrogen protection, hydroxyl value
It is added in three-necked flask, is heated to for the polyethylene oxide polyol of 450mg KOH/g, 36.0g phosphorus oxychloride and 200g toluene
50 DEG C and 1h is kept, is then heated to reflux until HCl gas discharges.It is cooled to room temperature, it is polynary that flame retarding polyether is obtained after washing
Alcohol.
2, the preparation of fire-retardant polyisocyanates
(1), the tetramethyl ammonium hydroxide solution for being under nitrogen protection, 2mol/L by 9.0g distilled water and 0.5mL concentration
It is added to 109.5gN after mixing, in dinethylformamide, obtains solution A；Under agitation, by 22.1g γ-ammonia
Propyl-triethoxysilicane and 12.0g phenyl triethoxysilane are slowly added dropwise in solution A, are warming up to 50 DEG C of reaction 8h, obtain
To solution B；91.19g hexamethyldisiloxane is added in solution B, after reacting 3h, through vacuum distillation, washing and drying, obtains
The degree of branching is 0.63, and the equal relative molecular weight of weight is 8000 through blocking containing amino and phenyl hyperbranched polyorganosiloxane.
(2), under the conditions of stirring and nitrogen protection, by 30g polyisocyanates and 300gN, dinethylformamide is added
In three-necked flask, 2.0g is added dropwise through sealing end and reacts 3h at a temperature of 0 DEG C with phenyl hyperbranched polyorganosiloxane containing amino, then
50 DEG C are warming up to the reaction was continued 4h, flame retardant type polyisocyanates is prepared after vacuum distillation.
3, the preparation of rigid polyurethane foam
It is 300 by 100g number-average molecular weight, hydroxyl value is polyethylene oxide polyol, the 50g flame retarding polyether of 270mg KOH/g
Polyalcohol, 50g HCFC-141b, 0.01g foam stabiliser B8870 and 0.02g dibutyl tin dilaurate are quick at 20 DEG C
It being uniformly mixed, fire-retardant polyisocyanates is added, the molar ratio of the fire-retardant polyisocyanates and all polyalcohols is 1.02:1,
High-speed stirred, which is injected after mixing in 15 DEG C of molds, to foam, and is cured at 20 DEG C up to flame retarded rigid polyurethane foams plastics.
Embodiment 2
1, the preparation of flame retardant polyether polyol
It is 400 by 10.0g melamine, the equal relative molecular weight of 25.0g number under the conditions of nitrogen protection, hydroxyl value 550mg
Polyoxypropylene polyol, 18.0g phosphorus oxychloride and the 250g dimethylbenzene of KOH/g is added in three-necked flask, is heated to 70 DEG C simultaneously
1h is kept, is then heated to reflux until HCl gas discharges.It is cooled to room temperature, flame retardant polyether polyol is obtained after washing.
2, the preparation of fire-retardant polyisocyanates
(1), under nitrogen protection, 9.0g distilled water is added with 1mL concentration for the hydrochloric acid solution of 2mol/L after mixing
Enter into 109.5g n,N-Dimethylformamide, obtains solution A；Under agitation, by 22.1g gamma-aminopropyl-triethoxy
Silane and 48.0g phenyl triethoxysilane are slowly added dropwise in solution A, are warming up to 60 DEG C of reaction 10h, obtain solution B；Molten
121.79g hexamethyldisiloxane is added in liquid B, after reacting 6h, through vacuum distillation, washing and drying, obtaining the degree of branching is
0.75, the equal relative molecular weight of weight is 12000 through blocking containing amino and phenyl hyperbranched polyorganosiloxane.
(2), under the conditions of stirring and nitrogen protection, by 30g polyisocyanates and 600gN, dinethylformamide is added
In three-necked flask, 0.5g is added dropwise through sealing end and reacts 5h at a temperature of 25 DEG C with phenyl hyperbranched polyorganosiloxane containing amino, with
After be warming up to 70 DEG C the reaction was continued 6h, flame retardant type polyisocyanates is prepared after vacuum distillation.
3, the preparation of rigid polyurethane foam
It is 800 by 100g number-average molecular weight, hydroxyl value is polyoxypropylene polyol, the 50g flame retarding polyether of 520mg KOH/g
Polyalcohol, 5g pentamethylene, 5g foam stabiliser L6950 and 2.5g triethylenediamine are quickly uniformly mixed at 60 DEG C,
Fire-retardant polyisocyanates is added, the molar ratio of the fire-retardant polyisocyanates and all polyalcohols is 3:1, and high-speed stirred is uniformly mixed
It injects in 70 DEG C of molds and foams afterwards, cured at 100 DEG C up to flame retarded rigid polyurethane foams plastics.
Embodiment 3
1, the preparation of flame retardant polyether polyol
It is 350 by 10.0g melamine, the equal relative molecular weight of 29.3g number under helium protective condition, hydroxyl value 500mg
Polytetrahydrofuran ethoxylated polyhydric alcohol, 20.2g phosphorus oxychloride and the 250g dimethylbenzene of KOH/g is added in three-necked flask, is heated to 70 DEG C
And 1h is kept, it is then heated to reflux until HCl gas discharges.It is cooled to room temperature, flame retardant polyether polyol is obtained after washing.
2, the preparation of fire-retardant polyisocyanates
(1), under helium protection, 9g distilled water is uniformly mixed with the potassium hydroxide solution that 0.75ml concentration is 2mol/L
After be added in 109.5g n,N-Dimethylformamide, obtain solution A；Under agitation, by 22.1g γ-three second of aminopropyl
Oxysilane and 44.0g phenyl triethoxysilane are slowly added dropwise in solution A, are warming up to 55 DEG C of reaction 9h, obtain solution B；
54.32g trim,ethylchlorosilane is added in solution B, after reacting 4h, through vacuum distillation, washing and drying, obtaining the degree of branching is
0.68, the equal relative molecular weight of weight is 9000 through blocking containing amino and phenyl hyperbranched polyorganosiloxane.
(2), under stirring and helium protective condition, 30g polyisocyanates and 400g n,N-Dimethylformamide are added
In three-necked flask, 0.7g is added dropwise through sealing end and reacts 4h at a temperature of 13 DEG C with phenyl hyperbranched polyorganosiloxane containing amino, with
After be warming up to 60 DEG C the reaction was continued 5h, flame retardant type polyisocyanates is prepared after vacuum distillation.
3, the preparation of rigid polyurethane foam
It is 550 by 100g number-average molecular weight, hydroxyl value is 395mg KOH/g polytetrahydrofuran ethoxylated polyhydric alcohol, 50g flame retarding polyether
Polyalcohol, 2.5g water, 2.5g foam stabiliser AK8805 and 1.2g dibutyltin diacetate are quickly stirred at 45 DEG C
It is even, fire-retardant polyisocyanates is added, the molar ratio of the fire-retardant polyisocyanates and all polyalcohols is 2:1, high-speed stirred mixing
It foams, cures at 80 DEG C up to flame retarded rigid polyurethane foams plastics in 60 DEG C of molds of injection after uniformly.
Embodiment 4
1, the preparation of flame retardant polyether polyol
It is 400 by 10.0g melamine, the equal relative molecular weight of 40.3g number under neon protective condition, hydroxyl value 550mg
Polytetrahydrofuran ethoxylated polyhydric alcohol, 30.2g phosphorus oxychloride and the 250g acetonitrile of KOH/g is added in three-necked flask, is heated to 60 DEG C simultaneously
3h is kept, is then heated to reflux until HCl gas discharges.It is cooled to room temperature, flame retardant polyether polyol is obtained after washing.
2, the preparation of fire-retardant polyisocyanates
(1), under neon protection, after mixing for 2mol/L sodium hydroxide solution by 9g distilled water and 0.5mL concentration
It is added in 219.0g n,N-Dimethylformamide, obtains solution A；Under agitation, by 22.1g γ-three ethoxy of aminopropyl
Base silane and 47.0g phenyl triethoxysilane are slowly added dropwise in solution A, are warming up to 58 DEG C of reaction 10h, obtain solution B；?
81.48g trim,ethylchlorosilane is added in solution B, after reacting 6h, through vacuum distillation, washing and drying, obtaining the degree of branching is
0.75, the equal relative molecular weight of weight is 9000 through blocking containing amino and phenyl hyperbranched polyorganosiloxane.
(2), under stirring and neon protective condition, 30g polyisocyanates and 500g n,N-Dimethylformamide are added
In three-necked flask, 0.75g is added dropwise through sealing end and reacts 3h at a temperature of 25 DEG C with phenyl hyperbranched polyorganosiloxane containing amino, with
After be warming up to 60 DEG C the reaction was continued 4h, flame retardant type polyisocyanates is prepared after vacuum distillation.
3, the preparation of rigid polyurethane foam
It is 800 by 100g number-average molecular weight, hydroxyl value is polyethylene oxide polyol, the 30g flame retarding polyether of 520mg KOH/g
Polyalcohol, 5g pentamethylene, 5g foam stabiliser AK8805 and 2.5g stannous octoate are quickly uniformly mixed at 60 DEG C, are added
The molar ratio of fire-retardant polyisocyanates, the fire-retardant polyisocyanates and all polyalcohols is 1.5:1, and high-speed stirred is after mixing
It injects in 55 DEG C of molds and foams, cured at 75 DEG C up to flame retarded rigid polyurethane foams plastics.
Comparative example 1
The preparation of rigid polyurethane foam
By 150g polyethylene oxide polyol (manufacturer is Shanghai Dongda Chemical Co., Ltd., model SD301A),
50g HCFC-141b, 0.01g foam stabiliser B8870 and 0.02g dibutyl tin dilaurate are quickly stirred at 20 DEG C
Uniformly, the molar ratio of addition polyisocyanates, the polyisocyanates and all polyalcohols is 1.02:1, and high-speed stirred is uniformly mixed
It injects in 15 DEG C of molds and foams afterwards, cured at 20 DEG C up to non-modified rigid polyurethane foam.
Comparative example 2
1, prepared by flame retardant polyether polyol
It is 300 by 10.0g melamine, the equal relative molecular weight of 60.0g number by quality under the conditions of nitrogen protection, hydroxyl value
It is added in three-necked flask for the polyether polyol and 36.4g phosphorus oxychloride of 450mg KOH/g, is heated to 50 DEG C and keeps 1h, so
After be heated to reflux until HCl gas discharges.It is cooled to room temperature, flame retardant polyether polyol is obtained after washing.
2, the preparation of rigid polyurethane foam
100g polyethylene oxide polyol, 50g flame retardant polyether polyol, 50g HCFC-141b, 0.01g foam are stablized
Agent B8870 and 0.02g dibutyl tin dilaurate are quickly uniformly mixed at 20 DEG C, and polyisocyanates (factory is added
Family is Wanhua Chemical Group Co., Ltd., model polymeric MDI PM200), the polyisocyanates and all polyalcohols
Molar ratio is 1.02:1, and high-speed stirred, which is injected after mixing in 15 DEG C of molds, to foam, and is cured at 20 DEG C up to hard polyurethane
Ester foamed plastic.
Comparative example 3
1, the preparation of fire-retardant polyisocyanates
(1), the tetramethyl ammonium hydroxide solution for being under nitrogen protection, 2mol/L by 9.0g distilled water and 0.5mL concentration
It is added in 109.5g n,N-Dimethylformamide after mixing, obtains solution A；Under agitation, by 22.1g γ-ammonia
Propyl-triethoxysilicane and 12.0g phenyl triethoxysilane are slowly added dropwise in solution A, are warming up to 50 DEG C of reaction 8h, obtain
To solution B；Hexamethyldisiloxane is added in solution B, after reacting 3h, through vacuum distillation, washing and drying, obtains the degree of branching
It is 0.63, the equal relative molecular weight of weight is 8000 through blocking containing amino and phenyl hyperbranched polyorganosiloxane.
(2), under the conditions of stirring and nitrogen protection, by 30g polyisocyanates and 300gN, dinethylformamide is added
In three-necked flask, 2.0g is added dropwise through sealing end and reacts 3h at a temperature of 0 DEG C with phenyl hyperbranched polyorganosiloxane containing amino, then
50 DEG C are warming up to the reaction was continued 4h, flame retardant type polyisocyanates is prepared after vacuum distillation.
2, the preparation of rigid polyurethane foam
By 150g polyethylene oxide polyol, 50g HCFC-141b, 0.01g foam stabiliser B8870 and 0.02g February
Dilaurylate is quickly uniformly mixed at 20 DEG C, and fire-retardant polyisocyanates is added, the fire-retardant polyisocyanates and institute
Have polyalcohol molar ratio be 1.02:1, high-speed stirred, which is injected after mixing in 15 DEG C of molds, to foam, at 20 DEG C curing be
Obtain rigid polyurethane foam.
Effect example
Embodiment 1-4 and comparative example 1-3 resulting product are tested for the property, specific test data is as shown in table 1.
Table 1
Note: polyether polyol limit oxygen index is the index of flame retardant polyether polyol, testing standard are as follows: GB/T
16581-1996；
Limit oxygen index is the index of flame retarded rigid polyurethane foams plastics, testing standard are as follows: ASTM-D2863-
2000；
The testing standard of compressive strength is GB8813-88；
The testing standard of smoke density is GB/T 8323-2008；
The testing standard of density is GB/T6343-1995.
As shown in Table 1: being steeped using hard prepared by modified polyether polyol or modified polyisocyanates
The oxygen index (OI) of foam body is increased, while when modified polyisocyanates pure and mild using modified polyether polyols, rigid foam
The limit oxygen index highest of body.Show the resistance that hard foam can be significantly improved to the pure and mild modified polyisocyanate of polyether polyols
Fire performance；UL-94 combustion testing is tested with compressive strength there is also similar trend simultaneously, when illustrating while be modified to the two,
The comprehensive performance of hard foam increases；In addition, simultaneously modified polyisocyanate pure and mild to polyether polyols when, hard bubble
The smoke density of foam body will be far below comparative example 1, illustrate the modified smoke amount for advantageously reducing hard foam；Finally, according to cigarette
Density measurement is it is found that be only modified polyisocyanates, and can be reduced using its preparation rigid polyurethane foam
Its smoke density.
Claims (14)
1. a kind of flame retarded rigid polyurethane foams plastics, which is characterized in that it is made by raw material, and the raw material includes following weight
The component of part: 100 part of first polyether polyol, 5-50 parts of flame retardant polyether polyols, 0.01-5 parts of foaming agents, 0.01-5 parts of foams
Stabilizer, the first catalyst of 0.02-2.5 part and fire-retardant polyisocyanates, the fire-retardant polyisocyanates with " described first is poly-
The molar ratio of ethoxylated polyhydric alcohol and the flame retardant polyether polyol " total amount is 1.02:1-3:1；
The flame retardant polyether polyol is made by raw material, and raw material includes following components in parts by weight: 10 parts of melamines, 25-60
The second polyether polyol of part, 18-36 parts of phosphorus oxychloride and 200-250 parts of solvents；
The fire-retardant polyisocyanates is made by raw material, and raw material includes the component of following parts by weight: 0.5-2 parts of hyperbranched poly silicon oxygen
Alkane, 30 parts of polyisocyanates and 300-600 parts of n,N-Dimethylformamide；
The hyperbranched polyorganosiloxane is made by raw material, and raw material includes such as following components: water, the second catalyst, N, N- dimethyl
Formamide, amino-trialkoxy silane, phenyl trialkoxysilane, end-capping reagent, the water, second catalyst, the N,
Dinethylformamide, the amino-trialkoxy silane, the phenyl trialkoxysilane, the end-capping reagent molar ratio be
10:(0.02-0.04): (30-60): 2:(1-4): (10-15).
2. flame retarded rigid polyurethane foams plastics as described in claim 1, which is characterized in that first polyether polyol or
Second polyether polyol is in polyethylene oxide polyol, polyoxypropylene polyol and polytetrahydrofuran ethoxylated polyhydric alcohol
It is one or more；
And/or the hydroxyl value of first polyether polyol is 270-520mg KOH/g；
And/or the equal relative molecular weight of number of first polyether polyol is 300-800；
And/or the hydroxyl value of second polyether polyol is 450-550mg KOH/g；
And/or the equal relative molecular weight of number of second polyether polyol is 300-400；
And/or the foaming agent is one of a fluorine dichloroethanes, pentane, pentamethylene and water or a variety of；
And/or institute's foam stabiliser is in foam stabiliser B8870, foam stabiliser L6950 and foam stabiliser AK8805
It is one or more；
And/or first catalyst is triethylenediamine, dibutyl tin dilaurate, stannous octoate, triethylamine, three second
One of hydramine and dibutyltin diacetate are a variety of；
And/or the solvent is one of toluene, dimethylbenzene and acetonitrile or a variety of；
And/or the degree of branching of the hyperbranched polyorganosiloxane is 0.63-0.75；
And/or the equal relative molecular weight of weight of the hyperbranched polyorganosiloxane is 8000-12000；
And/or the water is distilled water；
And/or second catalyst be hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide,
One of sodium hydroxide and potassium hydroxide are a variety of；
And/or the amino-trialkoxy silane is 3- TSL 8330 and/or gamma-aminopropyl-triethoxy
Silane；
And/or the phenyl trialkoxysilane is phenyltrimethoxysila,e and/or phenyl triethoxysilane；
And/or the end-capping reagent is hexamethyldisiloxane, trim,ethylchlorosilane, tri-phenyl chloride and chlorotriethyl silane
One of or it is a variety of.
3. flame retarded rigid polyurethane foams plastics as claimed in claim 2, which is characterized in that first polyether polyol
Hydroxyl value is 395mg KOH/g；
The equal relative molecular weight of number of first polyether polyol is 550；
The hydroxyl value of second polyether polyol is 500mg KOH/g；
The equal relative molecular weight of number of second polyether polyol is 350；
The degree of branching of the hyperbranched polyorganosiloxane is 0.68；
The equal relative molecular weight of the weight of the hyperbranched polyorganosiloxane is 9000.
4. flame retarded rigid polyurethane foams plastics as described in claim 1, which is characterized in that the flame retardant polyether polyol
Dosage is 25 parts；
And/or the dosage of the foaming agent is 2.5 parts；
And/or the dosage of the foam stabiliser is 2.5 parts；
And/or the dosage of first catalyst is 1.2 parts；
And/or the fire-retardant polyisocyanates and " the pure and mild flame retardant polyether polyol of the first polyether polyols " total amount
Molar ratio is 2:1 or 1.5:1；
And/or the dosage of second polyether polyol is 29.3 parts or 40.3 parts；
And/or the dosage of the phosphorus oxychloride is 20.2 parts or 30.2 parts；
And/or the dosage of the hyperbranched polyorganosiloxane is 0.75 part；
And/or the dosage of the phenyl trialkoxysilane is 3.6 parts.
5. flame retarded rigid polyurethane foams plastics according to any one of claims 1-4, which is characterized in that the flame retarding polyether
Polyalcohol is made by following step:
(1) under an inert atmosphere, by the melamine, second polyether polyol, the phosphorus oxychloride and the solvent
Mixture heating, insulation reaction；
(2) it is heated to reflux to hydrogen chloride gas and discharges, obtain the flame retardant polyether polyol after cooling.
6. flame retarded rigid polyurethane foams plastics as claimed in claim 5, which is characterized in that in step (1), the indifferent gas
Atmosphere is helium, neon or nitrogen；
And/or in step (1), the temperature after heating is 50-70 DEG C；
And/or in step (1), the time of the insulation reaction is 1-3h；
And/or in step (2), the temperature after cooling is room temperature.
7. flame retarded rigid polyurethane foams plastics as claimed in claim 6, which is characterized in that in step (1), the indifferent gas
Atmosphere is nitrogen；
In step (1), the temperature after heating is 60 DEG C；
In step (2), the room temperature is 10-30 DEG C.
8. flame retarded rigid polyurethane foams plastics according to any one of claims 1-4, which is characterized in that the fire-retardant polyisocyanate
Cyanate is made by following step:
(1) under agitation, the amino-trialkoxy silane and the phenyl trialkoxysilane are added dropwise to solution A
In, it heats up, reaction obtains solution B；The solution A is the water, second catalyst and the n,N-Dimethylformamide
Mixed solution；
(2) end-capping reagent is added in the solution B, reacts, obtains the hyperbranched polyorganosiloxane；
(3) it is stirring under inert atmosphere conditions, the hyperbranched polyorganosiloxane made from step (2) is being added dropwise to described
In polyisocyanates and the mixed solution of the n,N-Dimethylformamide, after first set reaction, then heat up second of progress
It reacts up to the fire-retardant polyisocyanates.
9. flame retarded rigid polyurethane foams plastics as claimed in claim 8, which is characterized in that in step (1), the solution A
It is made in the steps below: under an inert atmosphere, by " mixture of the water and second catalyst " and the N, N- diformazan
Base formamide mixes to obtain the final product；
And/or in step (1), the condition of the reaction is 50-60 DEG C of reaction 8-10h；
And/or in step (2), the time of the reaction is 3-6h；
And/or in step (3), the temperature of the first set reaction is 0-25 DEG C；
And/or in step (3), the time of the first set reaction is 3-5h；
And/or in step (3), the temperature of second secondary response is 50-70 DEG C；
And/or in step (3), the time of second secondary response is 4-6h.
10. flame retarded rigid polyurethane foams plastics as claimed in claim 9, which is characterized in that in step (1), the reaction
Condition be 55~58 DEG C of reaction 9h；
In step (2), the time of the reaction is 4h；
In step (3), the temperature of the first set reaction is 13 DEG C；
In step (3), the time of the first set reaction is 4h；
In step (3), the temperature of second secondary response is 60 DEG C；
In step (3), the time of second secondary response is 5h；
The inert atmosphere is helium, neon or nitrogen.
11. flame retarded rigid polyurethane foams plastics as claimed in claim 10, which is characterized in that the inert atmosphere is nitrogen
Gas.
12. a kind of preparation method of such as described in any item flame retarded rigid polyurethane foams plastics of claim 1-11 comprising
Following step:
(1) by first polyether polyol, the flame retardant polyether polyol, the foaming agent, the foam stabiliser and institute
The first catalyst is stated to be stirred；
(2) the fire-retardant polyisocyanates, mixing is added；
(3) it injects in mold and foams, cure up to the flame retarded rigid polyurethane foams plastics.
13. the preparation method of flame retarded rigid polyurethane foams plastics as claimed in claim 12, which is characterized in that step (1)
In, the mixed temperature is 20-60 DEG C；
And/or in step (3), the temperature of the mold is 15-70 DEG C；
And/or in step (3), the temperature of the curing is 20-100 DEG C.
14. the preparation method of flame retarded rigid polyurethane foams plastics as claimed in claim 13, which is characterized in that step (1)
In, the mixed temperature is 45 DEG C；
The temperature of the mold is 55 DEG C or 60 DEG C；
The temperature of the curing is 75 DEG C or 80 DEG C.
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| CN113402550B (en) * | 2021-06-18 | 2023-08-29 | 中国科学技术大学 | Flame-retardant polyol containing thiophosphonate, synthesis method thereof and application thereof in preparation of flame-retardant polyurethane soft foam |
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| CN114230752B (en) * | 2021-11-30 | 2023-07-18 | 山东一诺威新材料有限公司 | Intrinsic flame-retardant self-repairing polyurethane and preparation method thereof |
| CN117431684A (en) * | 2023-10-11 | 2024-01-23 | 广州汉德新材料股份有限公司 | Manufacturing method of water-splashing-preventing ultrathin soft knitted leather fabric |
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