CN110305281A - A kind of high-strength polyurethane hard bubble and preparation method thereof - Google Patents
A kind of high-strength polyurethane hard bubble and preparation method thereof Download PDFInfo
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- CN110305281A CN110305281A CN201910546662.1A CN201910546662A CN110305281A CN 110305281 A CN110305281 A CN 110305281A CN 201910546662 A CN201910546662 A CN 201910546662A CN 110305281 A CN110305281 A CN 110305281A
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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
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/5057—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- 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
- C08J9/04—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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- C—CHEMISTRY; METALLURGY
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention discloses a kind of high-strength polyurethane rigid foams, it is foamed and is made in high pressure foaming machine by the raw material comprising combined polyether component and isocyanate component, it is 100 parts of calculating with the gross mass number of combined polyether component, includes following component: (a) 5-30 parts of carbazole derivates amine polyether polyol A；(b) 20-50 parts of sucrose polyether polyol B；(c) 10-25 parts of toluenediamine polyether polyol C；(d) sucrose and glycerol are 10-30 parts of polyether polyol D of initiator；(e) 5-15 parts of low degree of functionality polyether polyol E；(f) surfactant 1.0-4.0 parts；(g) catalyst 1.5-5.0 parts；(h) water 0.8-4.0 parts；(i) foaming agent 5-30 parts.The characteristic that there is the foam the low density that feeds intake, high intensity, patience to become reduces client's production cost to be effectively reduced groundwater increment.
Description
Technical field
The invention belongs to polymeric foamed material technical fields, and in particular to a kind of to prepare low-density and high-strength rigid polyurethane
The combination material of foam material, and the polyurethane rigid foam material prepared using the combination material.
Technical background
Hard polyurethane foams have very high rate of closed hole, low-density, low thermally conductive system as a kind of polymer thermal insulative material
The advantages such as number, are widely used in heat preservation and insulation field.In general, polyurethane foam is as many such as refrigerators, hot water
The packing material of the household electrical appliances such as device needs to guarantee certain intensity to realize the effect as skeleton, while using in long-term
To guarantee the case where refrigerator is not in local contraction in journey.It is demonstrated experimentally that at identical conditions, the groundwater increment of foam is got over
Greatly, the core density of foam is bigger, and the ability of physical strength and resistance to deformation is stronger.
In recent years, due to environmental protection policy, the variation of the market demand, performance requirement of the client manufacturer to hard polyurethane foam
Also higher and higher.Guarantee that foam physics intensity is the important side that polyurethane foam is pursued while pursuing lower foam groundwater increment
One of to.
Carbazole and its derivative are very important azaaromatics, since it is with biggish conjugated system,
It is widely used in fields such as dyestuff, medicine, pesticide and photoelectric functional materials.By introducing rigid base in the molecular structure
Group, can effectively increase the free volume of molecule, improve the physical strength of substrate.The abscess of polyurethane foamed material is mainly
Polyhedron microcellular structure, each polyhedron are made of prism and film window.The physical structure intensity and abscess of prism and film
Homogeneity has a significant impact to the physical strength of foam.It is poly- that publication CN1908028 discloses a kind of low density and low thermal conductivity
Urethane rigid foam reacts the rigid poly urethanes bubble of preparation by combined polyether in the presence of composite catalyst with polyisocyanate
Foam does not influence the appearance property of product while realizing low density and low heat conduction rate, but current foaming system is close to the core of foam
The requirement of degree is lower, and hard polyurethane foam disclosed in the patent is not able to satisfy the increasing requirement of client manufacturer.
Summary of the invention
The purpose of the present invention is to provide a kind of high-strength polyurethane rigid foams and preparation method thereof, introduce one kind with click
Zole derivatives amine is the polyether polyol of initiator, and the structure of the polyether polyol can form complexity in polyurethane molecular
More Benzene Molecule structures, to greatly enhance foam structure intensity.The suitable polyether polyol combination of simultaneous selection and isocyanide
The polyurethane foam of the high physical strength of low-density is made in acid esters index.
For achieving the above object, the technical solution of the present invention is as follows:
A kind of high-strength polyurethane rigid foam, by the raw material comprising combined polyether component and isocyanate component
It foams and is made in high pressure foaming machine, be 100 parts of calculating with the gross mass number of combined polyether component,
Include following component:
(a) A5-30 parts of carbazole derivates amine polyether polyol；
(b) sucrose polyether polyol B20-50 parts；
(c) toluenediamine polyether polyol C10-25 parts；
(d) sucrose and glycerol are D10-30 parts of polyether polyol of initiator；
(e) E5-15 parts of low degree of functionality polyether polyol；
(f) surfactant 1.0-4.0 parts；
(g) catalyst 1.5-5.0 parts；
(h) water 0.8-4.0 parts；
(i) foaming agent 5-30 parts.
Wherein, isocyanate component and the mass ratio of combined polyether component are 110-160:100, preferably 120-140:
100。
In the present invention, the carbazole derivates amine polyether polyol A is with 3,6- bis- (4- aminophenyl) -9- hydrogen -
Carbazole is initiator and oxyalkylene through polyether polyol made from addition, and hydroxyl value is 400-460 mgKOH/g.
(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole structural formula are as follows:
The structure of the carbazole derivates amine polyether polyol A can indicate are as follows:
In the present invention, the preparation of the carbazole derivates amine polyether polyol A is comprised the steps of:
1) (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole aqueous solution (3~10%wt) and partial oxidation alkene is (excellent
Ring selection oxidative ethane) mixing, 60~90 DEG C self-catalyzed reaction 2~4 hours, then raise temperature to 90~120 DEG C react 2~4 hours；
2) alkali metal hydroxide (preferably potassium hydroxide) aqueous solution (20~60%wt) is added into step 1), mixing is equal
Vacuum dehydration after even, is added remaining oxyalkylene (preferably propylene oxide), is warming up to 100~130 DEG C and reacts 1~2 hour,
It then proceedes to be warming up to 130~140 DEG C of reactions 1~2 hour；
3) into step 2), addition appropriate amount of acid neutralizes (preferably phosphoric acid), dewatering and filtering removes potassium ion, finished product polyethers,
Hydroxyl value 400-460, testing standard GB/T 12008.3-1989.
Preferably, in above-mentioned preparation method, 3,6- bis- (4- aminophenyl) -9- hydrogen-carbazole and oxyalkylene mass ratio
For 1:1.5~2, the oxyalkylene that the oxyalkylene (optimization ethylene oxide) and step 2) that wherein step 1) is added are added is (preferably
Propylene oxide) mass ratio be 1:1~2.
In the preparation method of above-mentioned polyether polyol A by way of feeding intake step by step, obtain the hydrogen on amino sufficiently
Reaction, ensure that the high functionality of polyether polyol；Meanwhile the method for fractional steps can in time release the heat of system, prevent heat
Amount assembles and causes implode.
Preferably, in above-mentioned preparation method, the alkali of addition in 3,6- bis- (4- aminophenyl) -9- hydrogen-carbazole and step 1)
The mass ratio for the acid being added in metal hydroxides and step 2) is (15~20): 1:1.75.
In the present invention, 3, the 6- bis- (4- aminophenyl) -9- hydrogen-carbazole is the preparation method comprises the following steps: comprise the steps of:
1) N- bromo-succinimide solution is added into carbazole solution, is stirred to react 2.5~4 hours；It is washed out, takes
Organic phase is dry (such as the desiccant dryness such as anhydrous magnesium sulfate), removes solvent and obtains crude product；By crude product recrystallization, drying
Obtain bis- bromo carbazole of 3,6-；
2) it under an inert atmosphere, is added for reactant into salt with 3,6-, bis- bromo carbazole, p-aminophenyl boric acid
It is reacted under agent, active palladium catalyst and solvent existence condition；Then reaction solution is poured into water, obtains black solid；It is black
It is purified after the washing of color solid, obtains (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole.
In (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparation method, the solvent of carbazole solution is two in step 1)
One of chloromethanes, chloroform or tetrachloroethanes, concentration are 0.4~1.2mol/L；N- bromo-succinimide solution
Solvent is N, N '-dimethyl formamide, N, N '-dimethyl acetamide or N-Methyl pyrrolidone, and concentration is 8~14mol/L；Click
The mole dosage ratio of azoles and N- bromo-succinimide is 0.9~1:2.
In (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparation method, acetone and n-hexane are used in step 1)
Mixed solution recrystallizes crude product, and volume ratio is 1~1.5:3~5, and it is small that 8~12 are dried in vacuo at 65~85 DEG C
When.
In (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparation method, active palladium described in step 2) is four
(triphenyl phosphorus) palladium or palladium carbon.
In (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparation method, salt forming agent described in step 2) is carbonic acid
Potassium or sodium carbonate, the solvent are Isosorbide-5-Nitrae-dioxane and water, and the two volume ratio is 1.5~4:1.
It is 3,6-, bis- bromo carbazole in step 2), right in (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparation method
Amino phenyl boric acid, salt forming agent, active palladium, 1,4- dioxane, water usage ratio be 1mol:2.1~2.4mol:2.1~
2.4mol:0.045~0.065mol:4~4.2L:2~2.2L.
In (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparation method, reaction temperature is 80~90 in step 2)
DEG C, the reaction time is 20~30 hours.
In high-strength polyurethane rigid foam of the invention, the polyether polyol A is to be with carbazole derivates amine
Initiator and ethylene oxide and propylene oxide are made through addition reaction, wherein the ratio of ethylene oxide and propylene oxide is 1；1~
2.Polyether polyol B is that sucrose is that initiator and propylene oxide addition reaction are made.Polyether polyol C is to be with toluenediamine
Beginning agent and propylene oxide addition reaction are made.It is initiator and propylene oxide through addition that polyether polyol D, which is using sucrose and glycerol,
Reaction is made.Polyether polyol E is obtained through addition reaction using glycerol as initiator and propylene oxide.
Preferably, polyether polyol B hydroxyl value is 360-420mgKOH/g, and polyether polyol C hydroxyl value is 390-
460mgKOH/g, polyether polyol D hydroxyl value are 420-490mgKOH/g, and the hydroxyl value of polyether polyol E is 180-260mgKOH/g.
In high-strength polyurethane rigid foam of the invention, surfactant used in the present invention is the Dehua Jiangsu Mei Si
B8525, B8545 etc. of the AK8830 of limited liability company, Evonik.These surfactant nucleations are strong, and stability is good,
Be conducive to prepare the hard polyurethane foams of uniform foam cell.
The catalyst is selected from amines catalyst and/or organic metal salt catalyst, preferably pentamethyl diethylidene three
Amine, HP1038, triethylenediamine, dimethylethanolamine, N, N- dimethyl cyclohexyl amine, triethylene diamine, triethylamine, 1,4- bis-
Methyl piperazine, N, N- dimethyl benzylamine, double dimethylamino ethyl ethers, Hexahydrotriazine, potassium acetate, isooctyl acid potassium, in stannous octoate
One or more, more preferably triethylene diamine, N, N- dimethyl cyclohexyl amine, pentamethyldivinyltriamine, Hexahydrotriazine
With it is one or more in potassium acetate；
The foaming agent is selected from the pentamethylene of Zibo Xin Rong Chemical Industry Science Co., Ltd.
The high-strength polyurethane rigid foam preparation method is as steps described below:
1) combined polyether glycol, surfactant, catalyst and water are uniformly mixed and obtain polyether polyol mixtures.
2) foaming agent is further uniformly mixed with the polyether polyol mixtures mixed in step 1.
3) mixture made from step 2 is mixed with high pressure foaming machine with isocyanates, that is, prepares rigid poly urethanes bubble
Foam.It is preferred that the operating condition of high pressure foaming machine are as follows: 20 ± 4 DEG C of material temperature, 125 ± 25bar of operating pressure.
The isocyanates is polymeric MDI (poly methylene poly phenyl poly isocyanate), and NCO content is 30~32%.
Adoptable polymeric isocyanate includes PM-200, PM-2010 and PM-400 of Wanhua Chemical Group Co., Ltd..
The positive effect of the present invention is:
1) present invention in hard polyurethane foams combined polyether mainly by introducing using carbazole derivates amine as initiator
The mode of novel polyether polyol improve the physical structure intensity of abscess so that foam energy under Low perfusion amount low-density
There is good physical strength.(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole ethyl polyethylene-oxide polyoxypropylene polyol is poly-
Complicated more Benzene Molecule structures can be formed in urethane molecule, to greatly enhance foam structure intensity.
2) present invention is applied to hard polyurethane foams using the polyether polyol that big conjugated structure is initiator synthesis
Thinking does not occur in the industry cycle.
3) foam produced by the present invention is obviously higher than low density foam physical strength made from general polyether polyol,
30kg/m3Core density under conditions of, the polyether polyol containing carbazole derivates and combined polyether is adjusted by introducing,
Intensity can achieve 165KPa or more, and thermal coefficient is suitable, while without sacrificing other performance.
Detailed description of the invention:
Fig. 1 is (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole hydrogen nuclear magnetic resonance spectrogram prepared by example 1.
Specific embodiment
Embodiment of the present invention is further illustrated below with reference to embodiment.But the present invention is not limited to listed implementations
Example should also include other any well known changes in interest field of the presently claimed invention.
By carbazole derivates amine initiator polyether polyol, common polyether, surfactant, catalyst, water is in proportion
Mixing foaming agent is made of pentamethylene, and fraction scale is added in combined polyether by weight, at ambient temperature by foaming agent and group
It closes polyethers to be uniformly mixed, obtained mixture is sufficiently mixed system by both certainty ratios through HENNECK high pressure foaming machine and isocyanates
Standby hard polyurethane foam.The batch can temperature of high pressure foaming machine is set as 16~22 DEG C, and pipette tips temperature is 20~25 DEG C, pipette tips pressure
Power is 110~135KPa, and flow is 300~700 g/s.
Polyether polyol A: being initiator and ethylene oxide and propylene oxide through addition reaction system using carbazole derivates amine
, hydroxyl value 400-460mgKOH/g.
Polyether polyol B: being initiator and propylene oxide through addition reaction system, hydroxyl value 360-420 mgKOH/g using sucrose.
Polyether polyol C: it is made using toluenediamine as initiator and propylene oxide through addition reaction, hydroxyl value 390-460
mgKOH/g。
Polyether polyol D: it is made using sucrose and glycerol as initiator and propylene oxide through addition reaction, hydroxyl value 420-490
mgKOH/g。
Polyether polyol E: it is made using glycerol as initiator and propylene oxide through addition reaction, hydroxyl value 180-260
mgKOH/g。
Main material used in the present invention and reagent source are as follows:
Foaming agent: pentamethylene, Zibo Xin Rong Chemical Industry Science Co., Ltd
Isocyanates: PM200, Wanhua Chemical Group Co., Ltd.
Surfactant: AK8830, Nanjing Dymatic Shichuang Chemical Co., Ltd.
Catalyst: triethylene diamine, N, N- dimethyl cyclohexyl amine, pentamethyldivinyltriamine, Hexahydrotriazine and acetic acid
Potassium, air chemical industry
Polyether polyol A is prepared by the embodiment of the present invention, other polyether polyol are purchased from ten thousand Hua Huaxue (Ningbo) Rong Wei:
(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparating example 1: step are as follows:
1) under the conditions of room temperature, physical agitation, into the dichloromethane solution (0.8mol/L) of carbazole with 4mL/min's
The N of N- bromo-succinimide is added dropwise in speed, and N '-dimethyl formamide solution (10 mol/L) stirs 3.5 hours；Then will
The distillation of above-mentioned solution same volume is washed 4 times, and organic phase is obtained, dry with 10g anhydrous magnesium sulfate；Then it depressurizes at room temperature
It is that -0.09 MPa steams the solvent in organic phase to vacuum degree, obtains light gray crude product；Mixing with acetone and n-hexane is molten
Liquid (volume ratio 1:2) recrystallizes light gray crude product；Final product is dried in vacuo 11 hours at 70 DEG C, obtains grey
Bis- bromo carbazole of bulk crystals, that is, 3,6-；Wherein, carbazole: the mole dosage ratio of N- bromo-succinimide is 0.9:2；
2) under an inert atmosphere, with 3,6-, bis- bromo carbazole, p-aminophenyl boric acid be reactant, sodium carbonate be at
Salt agent, tetrakis triphenylphosphine palladium are catalyst, and Isosorbide-5-Nitrae-dioxane and distilled water are solvent, are mixed under magnetic stirring, are heated up
It is reacted 21 hours to 90 DEG C；Wherein, 3,6-, bis- bromo carbazole, p-aminophenyl boric acid, potassium carbonate, tetrakis triphenylphosphine palladium, Isosorbide-5-Nitrae-
Dioxane, distilled water usage ratio be 1mol:2.2mol:2.1mol:0.06mol:4L:2.2L.Then by reaction solution
It pours into distilled water, obtains black solid；Technology is used column chromatography after black solid washing to be purified, and white powder can be obtained
End is (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole, and qualitative by nuclear-magnetism, hydrogen nuclear magnetic resonance spectrogram is as shown in Figure 1.
(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparating example 2: step are as follows:
1) under the conditions of room temperature, physical agitation, into the low boiling point chloroform soln (0.4mol/L) of carbazole with
The N of N- bromo-succinimide is added dropwise in the speed of 7.5mL/min, and it is small to stir 2.5 for N '-dimethyl formamide solution (8mol/L)
When；Then the distillation of above-mentioned solution same volume is washed 5 times, obtains organic phase, it is dry with 10g anhydrous magnesium sulfate；Then
It is decompressed to 0.095MPa at room temperature and steams solvent in organic phase, obtains light gray crude product；With the mixing of acetone and n-hexane
Solution (volume ratio 1:3) recrystallizes light gray crude product；Final product is dried in vacuo 8 hours at 85 DEG C, obtains ash
Color bulk crystals, that is, bis- bromo carbazole of 3,6-；Wherein, carbazole: the mole dosage ratio of N- bromo-succinimide is 0.9:1；
2) under an inert atmosphere, with 3,6-, bis- bromo carbazole, p-aminophenyl boric acid be reactant, potassium carbonate be at
Salt agent, tetrakis triphenylphosphine palladium are catalyst, and Isosorbide-5-Nitrae-dioxane and distilled water are solvent, are mixed under magnetic stirring, are heated up
It is reacted 29.5 hours to 82 DEG C；Then reaction solution is poured into distilled water, obtains black solid；Column is used after black solid washing
Chromatography technology is purified, and (4- the aminophenyl) -9- of i.e. 3, the 6- of white powder bis- hydrogen-carbazole can be obtained；Wherein, 3,6-
Two bromo carbazoles, p-aminophenyl boric acid, potassium carbonate, tetrakis triphenylphosphine palladium, 1,4- dioxane, distilled water usage ratio be
1mol:2.1mol:2.1mol:0.045mol:4L:2L.
(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole preparating example 3: step are as follows:
1) under the conditions of room temperature, physical agitation, into the low boiling point chloroform soln (1.2mol/L) of carbazole with 8mL/
The N of N- bromo-succinimide is added dropwise in the speed of min, and N '-dimethyl formamide solution (14mol/L) stirs 4 hours；Then
The distillation of above-mentioned solution same volume is washed 5 times, organic phase is obtained, it is dry with 10g anhydrous magnesium sulfate；Then subtract at room temperature
Being depressed into vacuum degree is that -0.1 MPa steams solvent in organic phase, obtains light gray crude product；With the mixing of acetone and n-hexane
Solution (volume ratio 1:4) recrystallizes light gray crude product；Final product is dried in vacuo 12 hours at 85 DEG C, obtains ash
Color bulk crystals, that is, bis- bromo carbazole of 3,6-；Wherein, carbazole: the mole dosage ratio of N- bromo-succinimide is 0.9:2；
2) under an inert atmosphere, with 3,6-, bis- bromo carbazole, p-aminophenyl boric acid be reactant, potassium carbonate be at
Salt agent, tetrakis triphenylphosphine palladium are catalyst, and Isosorbide-5-Nitrae-dioxane and distilled water are solvent, are mixed under magnetic stirring, are heated up
It is reacted 29.5 hours to 90 DEG C；Then reaction solution is poured into distilled water, obtains black solid；Column is used after black solid washing
Chromatography technology is purified, and (4- the aminophenyl) -9- of i.e. 3, the 6- of white powder bis- hydrogen-carbazole can be obtained；Wherein, 3,6-
Two bromo carbazoles, p-aminophenyl boric acid, potassium carbonate, tetrakis triphenylphosphine palladium, 1,4- dioxane, distilled water usage ratio be
1mol:2.4mol:2.37mol:0.065mol:4.2L:2.2L.
Embodiment 1:
(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole is the preparation of the polyether polyol A1 of initiator:
1) by water (4420g) and 3, (4- the aminophenyl) -9- of 6- bis- hydrogen-carbazole (340g) is added in reaction kettle, nitrogen
Pressure testing is replaced, unlatching is stirred and heated to 70 DEG C.By the metered ethylene oxide 250g of flow 800g/h into reaction kettle.Then
110 DEG C, which are warming up to, after the reaction was continued 3h reacts 3h again.
2) addition 41.8g potassium hydroxide aqueous solution (50wt%) takes off vaccum dewatering 2h at 110 DEG C.By flow 600g/h
Metered propylene oxide 350g.135 DEG C, which are warming up to, after the reaction was continued 1.5h reacts 1.5h again.
3) phosphate aqueous solution for adding the 50wt% of 73.4g removes K ion, and processing obtains final product polyalcohol.Gained
It is 405mgKOH/g, testing standard GB/T that polyalcohol, which carries out titration test hydroxyl value using the method for phthalic anhydride esterification method,
12008.3-1989。
Embodiment 2:
(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole is the preparation of the polyether polyol A2 of initiator
1) by water (4420g) and 3, (4- the aminophenyl) -9- of 6- bis- hydrogen-carbazole (340g) is added in reaction kettle, nitrogen
Pressure testing is replaced, unlatching is stirred and heated to 60 DEG C.By the metered ethylene oxide 200g of flow 800g/h into reaction kettle.Then
90 DEG C, which are warming up to, after the reaction was continued 2h reacts 2h again.
2) 35.2g potassium hydroxide aqueous solution (50wt%) is added.Vaccum dewatering 2h is taken off at 100 DEG C.By flow 600g/h
Metered propylene oxide 250g.130 DEG C, which are warming up to, after the reaction was continued 1h reacts 1h again.
3) phosphate aqueous solution for adding the 50wt% of 61.6g removes K ion, and processing obtains final product polyalcohol.Gained
It is 457mgKOH/g, testing standard GB/T that polyalcohol, which carries out titration test hydroxyl value using the method for phthalic anhydride esterification method,
12008.3-1989。
Embodiment 3:
(4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole is the preparation of the polyether polyol A3 of initiator
1) by water (4420g) and 3, (4- the aminophenyl) -9- of 6- bis- hydrogen-carbazole (340g) is added in reaction kettle, nitrogen
Pressure testing is replaced, unlatching is stirred and heated to 90 DEG C.By the metered ethylene oxide 220g of flow 800g/h into reaction kettle.Then
120 DEG C, which are warming up to, after the reaction was continued 4h reacts 4h again.
2) 45.3g potassium hydroxide aqueous solution (50wt%) is added.Vaccum dewatering 2h is taken off at 130 DEG C.By flow 600g/h
Metered propylene oxide 300g.140 DEG C, which are warming up to, after the reaction was continued 2h reacts 2h again.
3) phosphate aqueous solution for adding the 50wt% of 79.3g removes K ion, and processing obtains final product polyalcohol.Gained
It is 427 mgKOH/g, testing standard GB/T that polyalcohol, which carries out titration test hydroxyl value using the method for phthalic anhydride esterification method,
12008.3-1989。
Embodiment 4
A kind of hard polyurethane foam preparation, raw material composition:
Polyether polyol used in this example are as follows:
(4- the aminophenyl) -9- of polyether polyol A1 3,6- bis- hydrogen-carbazole is starting, hydroxyl value 405mgKOH/g；
Polyether polyol B1 sucrose is initiator, hydroxyl value 385mgKOH/g；
Polyether polyol C1 toluenediamine is initiator, hydroxyl value 430mgKOH/g；
Polyether polyol D1 sucrose and glycerol are initiator, hydroxyl value 460mgKOH/g；
Polyether polyol E1 glycerol is initiator, hydroxyl value 188mgKOH/g；
According to the ratio of table 1, by polyether polyol A1-E1, surfactant, catalyst, water mixes foaming agent in proportion
It is made of, is proportionally added into combined polyether pentamethylene, be at ambient temperature uniformly mixed foaming agent and combined polyether, obtain
Mixture be sufficiently mixed through HENNECK high pressure foaming machine and isocyanates by both certainty ratios and prepare hard polyurethane foam.It is high
The batch can temperature of foam machine is set as 22 DEG C, and pipette tips temperature is 25 DEG C, and pipette tips pressure is 135KPa, flow 700g/s.
Embodiment 5
A kind of hard polyurethane foam preparation, preparation method is the same as embodiment 4
Polyether polyol used in this example are as follows:
(4- the aminophenyl) -9- of polyether polyol A2 3,6- bis- hydrogen-carbazole is starting, hydroxyl value 457mgKOH/g；
Polyether polyol B2 sucrose is initiator, hydroxyl value 415mgKOH/g；
Polyether polyol C2 toluenediamine is initiator, hydroxyl value 457mgKOH/g；
Polyether polyol D2 sucrose and glycerol are initiator, hydroxyl value 426mgKOH/g；
Polyether polyol E2 glycerol is initiator, hydroxyl value 225mgKOH/g.
Embodiment 6
A kind of hard polyurethane foam preparation, preparation method is the same as embodiment 4
Polyether polyol used in this example are as follows:
(4- the aminophenyl) -9- of polyether polyol A3 6- bis- hydrogen-carbazole is starting, hydroxyl value 427mgKOH/g；
Polyether polyol B3 sucrose is initiator, hydroxyl value 362mgKOH/g；
Polyether polyol C3 toluenediamine is initiator, hydroxyl value 398mgKOH/g；
Polyether polyol D3 sucrose and glycerol are initiator, hydroxyl value 490mgKOH/g；
Polyether polyol E3 glycerol is initiator, hydroxyl value 256mgKOH/g.
Comparative example 1
A kind of hard polyurethane foam preparation, preparation method are shown in Table 1. with embodiment 4, raw material composition
Comparative example 2
A kind of hard polyurethane foam preparation, preparation method are shown in Table 1. with embodiment 4, raw material composition
Table 1
The addition of appropriate amount novel polyether A can significantly improve foam physics intensity, when A content is when within 5-25%,
The content for increasing A is little on influencing on foam heating conduction while significantly improving foamy body.
Note:
1) foam core density measurement is according to standard: GB/T 6343-2009
Foam thermal conductivity is tested according to standard: GB/T 10295-2008
Foam compression strength test is according to standard: GB/T 8813-2008
Foam size stability test is according to standard: GB/T 8811-2008
2) raw material deal is calculated as mass fraction.
Claims (14)
1. a kind of high-strength polyurethane rigid foam, by the raw material comprising combined polyether component and isocyanate component in high pressure
It foams and is made in bubble machine, which is characterized in that be 100 parts with the gross mass number of combined polyether component and calculate, include following component:
(a) 5-30 parts of carbazole derivates amine polyether polyol A；
(b) sucrose polyether polyol B20-50 parts；
(c) toluenediamine polyether polyol C10-25 parts；
(d) sucrose and glycerol are D10-30 parts of polyether polyol of initiator；
(e) E5-15 parts of low degree of functionality polyether polyol；
(f) surfactant 1.0-4.0 parts；
(g) catalyst 1.5-5.0 parts；
(h) water 0.8-4.0 parts；
(i) foaming agent 5-30 parts.
2. high-strength polyurethane rigid foam according to claim 1, it is characterized in that: the carbazole derivates amine is poly-
Ethoxylated polyhydric alcohol A is more through polyethers made from addition as initiator and oxyalkylene using (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole
First alcohol, hydroxyl value 400-460mgKOH/g.
3. high-strength polyurethane rigid foam according to claim 1 or 2, it is characterized in that: the carbazole derivates amine
1) preparation of class polyether polyol A is comprised the steps of: (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole aqueous solution and portion
Point oxyalkylene, optimization ethylene oxide mixing, 60~90 DEG C self-catalyzed reaction 2~4 hours, then raise temperature to 90~120 DEG C
Reaction 2~4 hours；2) alkali metal hydroxide, preferably potassium hydroxide aqueous solution are added into step 1), after mixing vacuum
Dehydration, is added remaining oxyalkylene, preferably propylene oxide, is warming up to 100~130 DEG C and reacts 1~2 hour, then proceedes to rise
Temperature to 130~140 DEG C react 1~2 hour；3) neutralize to acid is added in step 2), preferably phosphoric acid, dewatering and filtering remove potassium from
Son, finished product polyethers；Preferably, the oxyalkylene mass ratio that the oxyalkylene and step 2) that step 1) is added are added is 1:1
~2；The mass ratio of (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole and oxyalkylene is 1:1.5~2.
4. high-strength polyurethane rigid foam according to claim 3, it is characterized in that: (the 4- aminobenzene of 3,6- bis-
Base) -9- hydrogen-carbazole is the preparation method comprises the following steps: comprise the steps of:
1) N- bromo-succinimide solution is added into carbazole solution, is stirred to react 2.5~4 hours；It is washed out, takes organic
It is mutually dry, it removes solvent and obtains crude product；By crude product recrystallization, it is dried to obtain bis- bromo carbazole of 3,6-；
2) salt forming agent, work under an inert atmosphere, are added for reactant with 3,6-, bis- bromo carbazole, p-aminophenyl boric acid
It is reacted under property palladium catalyst and solvent existence condition；Then reaction solution is poured into water, obtains black solid；Black solid
It is purified after washing, obtains (4- the aminophenyl) -9- of 3,6- bis- hydrogen-carbazole.
5. high-strength polyurethane rigid foam according to claim 4, it is characterized in that: in step 1) carbazole solution solvent
For one of methylene chloride, chloroform or tetrachloroethanes, concentration is 0.4~1.2mol/L；N- bromo-succinimide is molten
The solvent of liquid is N, N '-dimethyl formamide, N, N '-dimethyl acetamide or N-Methyl pyrrolidone, and concentration is 8~14mol/
L；The mole dosage ratio of carbazole and N- bromo-succinimide is 0.9~1:2.
6. high-strength polyurethane rigid foam according to claim 4, it is characterized in that: using acetone and just oneself in step 1)
The mixed solution of alkane recrystallizes crude product, and volume ratio is 1~1.5:3~5, and 8~12 are dried in vacuo at 65~85 DEG C
Hour.
7. the high-strength polyurethane rigid foam according to any one of claim 4-6, it is characterized in that:, it is characterized in that: step
It is rapid 2) described in active palladium be four (triphenyl phosphorus) palladiums or palladium carbon.
8. high-strength polyurethane rigid foam according to claim 7, it is characterized in that: salt forming agent described in step 2) is
Potassium carbonate or sodium carbonate, the solvent are Isosorbide-5-Nitrae-dioxane and water, and the two volume ratio is 1.5~4:1.
9. high-strength polyurethane rigid foam according to claim 8, it is characterized in that: 3,6-, bis- bromo click in step 2)
Azoles, p-aminophenyl boric acid, salt forming agent, active palladium, 1,4- dioxane, water usage ratio be 1mol:2.1~2.4mol:2.1
~2.4mol:0.045~0.065mol:4~4.2L:2~2.2L.
10. high-strength polyurethane rigid foam according to claim 4, it is characterized in that: reaction temperature is 80 in step 2)
~90 DEG C, the reaction time is 20~30 hours.
11. hard polyurethane foam according to claim 1, it is characterized in that: polyether polyol B be sucrose be initiator with
Propylene oxide addition reaction is made；Polyether polyol C is obtained through addition reaction using toluenediamine as initiator and propylene oxide；
Polyether polyol D is obtained through addition reaction using sucrose and glycerol as initiator and propylene oxide；Polyether polyol E is with glycerol
It is made for initiator and propylene oxide through addition reaction, it is preferable that polyether polyol B hydroxyl value is 360-420mgKOH/g, polyethers
Polyalcohol C hydroxyl value is 390-460mgKOH/g, and polyether polyol D hydroxyl value is 420-490mgKOH/g, the hydroxyl value of polyether polyol E
For 180-260mgKOH/g.
12. hard polyurethane foam according to claim 1, it is characterized in that: the catalyst be selected from amines catalyst and/
Or organic metal salt catalyst, preferably five methyl diethylentriamine, HP1038, triethylenediamine, dimethylethanolamine,
N, N- dimethyl cyclohexyl amine, triethylene diamine, triethylamine, 1,4- lupetazin, N, N- dimethyl benzylamine, double dimethylamino second
One of base ether, Hexahydrotriazine, potassium acetate, isooctyl acid potassium, stannous octoate are a variety of, more preferably triethylene diamine, N, N-
It is one or more in dimethyl cyclohexyl amine, pentamethyldivinyltriamine, Hexahydrotriazine and potassium acetate；The foaming agent is ring penta
Alkane.
13. hard polyurethane foam according to claim 1, it is characterized in that: isocyanate component and combined polyether component
Mass ratio be 110-160:100, preferably 120-140:100.
14. the preparation method of hard polyurethane foam according to claim 1 to 13 comprising the steps of: press
Each polyethers, surfactant, catalyst and water are uniformly mixed according to proportion and obtain polyether polyol mixtures, by foaming agent and is gathered
Ethoxylated polyhydric alcohol mixture is uniformly mixed, and isocyanates and foaming agent are mixed system with polyether polyol mixtures with high pressure foaming machine
Standby hard polyurethane foam, the preferably operating condition of high pressure foaming machine are as follows: 20 ± 4 DEG C of material temperature, 125 ± 25bar of operating pressure.
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