CN108264624A - Polyurethane composition polyethers, hard polyurethane foam and preparation method thereof - Google Patents
Polyurethane composition polyethers, hard polyurethane foam and preparation method thereof Download PDFInfo
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- CN108264624A CN108264624A CN201810049524.8A CN201810049524A CN108264624A CN 108264624 A CN108264624 A CN 108264624A CN 201810049524 A CN201810049524 A CN 201810049524A CN 108264624 A CN108264624 A CN 108264624A
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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
- C08G18/50—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
- C08G18/5063—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
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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
- C08J9/143—Halogen containing compounds
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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
- C08G2110/0025—Foam properties rigid
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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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to polyurethane material technical fields.The problems such as compressive strength density ratio that flame retardant property to solve polyurethane foam in the prior art is low, bad mechanical property, smoke amount are big, relatively low, relatively low oxygen index (OI) density ratio and larger smoke density.The present invention provides a kind of polyurethane composition polyethers, hard polyurethane foam and preparation method thereof；The polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：2 parts~5 parts of 30 parts~70 parts of melamine polyalcohol, 30 parts~70 parts of phosphorous-containing polyester dihydric alcohol, 10 parts~20 parts of smoke inhibition fire retardant, 10 parts~25 parts of physical blowing agent, 1 part~3 parts of foam stabilizer, 1 part~2 parts of chemical foaming agent and catalyst.The hard polyurethane foam includes component A and component B；The component B is poly methylene poly phenyl poly isocyanate；The weight ratio of the component A and component B is component A：Component B=1:1.0~1.7.The present invention has the characteristics that high compression-strength density ratio, hyperoxia exponential density ratio simultaneously.
Description
Technical field
The invention belongs to polyurethane material technical fields, and in particular to a kind of polyurethane composition polyethers, rigid poly urethanes bubble
Foam and preparation method thereof.
Background technology
Polyurethane foam is a kind of synthetic material of function admirable, it has many advantages, such as, and specific strength is high, thermal conductivity factor is small,
Under the promotion of the policies such as national energy-saving emission reduction, it is more and more widely used in fields such as building heat preservations.Without fire-retardant place
The polyurethane foam fire protecting performance of reason is poor, it is inflammable and burn when generate a large amount of smog, these smog often cause in fire
The principal element of injures and deaths.For this purpose, it generally requires to add a large amount of solid or liquid flame-proof into polyurethane foam in actual production
Material.
Solid fireproof material mainly has the oxide such as Sb of metal2O3Deng, metal hydroxides Al (OH)3With Mg (OH)2
Deng, Phos and phosphide, boride such as hydration zinc borate etc., storage stability is poor in the feed for such solid material, easily point
Layer, viscosity of sludge is big, reduces the processing performance of urethane raw, and mobile performance increases foamed material thermal conductivity factor, actual processing
Using being above restricted.
It is liquid flame-proof material to lead to be applied on the market.Liquid flame-proof material mainly has diethyl ethylphosphate, propyl
Dimethyl phosphonate, triethyl phosphate and tricresyl phosphate (2- chloro isopropyls) ester etc., such fire proofing are increasing polyurethane foam
There is also the mechanical performance for reducing foam while flame retardant property, increase the smoke amount during burning of foam, dramatically increase foam
Density of core material the shortcomings of, be embodied in relatively low compressive strength density ratio, relatively low oxygen index (OI) density ratio and larger
Smoke density.
So the challenge that existing polyurethane composition polyethers and hard polyurethane foam always exist in the application is
How while flame retardant property is improved relatively low thermal conductivity, relatively low smoke density, the relatively low density that feeds intake, higher pressure met
The requirement of the parameters such as contracting strength to density ratio and higher oxygen index (OI) density ratio.
Invention content
It is an object of the invention to solve technical problem in the prior art above at least one of, provide a kind of poly-
Urethane combined polyether, hard polyurethane foam and preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
30 parts~70 parts of alcohol, 30 parts~70 parts of phosphorous-containing polyester dihydric alcohol, 10 parts~20 parts of smoke inhibition fire retardant, physical blowing agent 10 parts~25
Part, 1 part~3 parts of foam stabilizer, 1 part~2 parts of chemical foaming agent and 2 parts~5 parts of catalyst.
Further, the component A includes the component of following parts by weight：36 parts of melamine polyalcohol, phosphorous-containing polyester binary
3.5 parts of 50 parts of alcohol, 13 parts of smoke inhibition fire retardant, 13 parts of physical blowing agent, 2 parts of foam stabilizer, 1.3 parts of chemical foaming agent and catalyst.
Further, the melamine polyalcohol is the polyalcohol that the polynary melamine of class is initiator, hydroxyl value 210 ±
10mgKOH/g, 6000 ± 1000mPas/25 DEG C of viscosity, acid value≤1.0mgKOH/g；The phosphorous-containing polyester dihydric alcohol be containing
Phosphorus fragrance binary member alcohol, the phosphorous fragrant binary member alcohol hydroxyl value is 190-200mgKOH/g, viscosity 2000-3500MPa
S/25 DEG C, acid value≤1mgKOH/g；Or the melamine polyalcohol is Jiangsu Chang Neng groups EDS-5083L；Described is phosphorous poly-
Ester dihydric alcohol is Beijing dolantin section innovative material DM2013.
Further, the smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；The even bubble
Agent for air LK443, air LK221, Mei Side AK-8805 and win wound B8462 in it is one or more；The chemical blowing
Agent is deionized water；The catalyst is in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
It is two or more.
A kind of hard polyurethane foam based on polyurethane composition polyethers, including component A and component B；The component B is more
Polymethylene polyphenyl polyisocyanates；The weight ratio of the component A and component B is component A：Component B=1:1.0~1.7.
Preferably, the weight ratio of the component A and component B is component A：Component B=1:1.2~1.7.
Preferably, the weight ratio of the component A and component B is component A：Component B=1:1.4~1.6.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A is 20~25 DEG C, and the time stirred in advance is 10min, is stirred for
Time is 0.5h~1h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
The present invention is relative to the advantageous effect of the prior art：
1st, surface temperature during polyurethane foam combustion can be reduced present invention introduces melamine structure, increases its thermal capacity,
Make the generating rate of burn rate and fuel gas reduce simultaneously, in the starting stage of burning, reacted with isocyanates fragment, pressed down
The generation of tobacco curing.Make the parameters such as the peak value of heat release rate, the peak value of cigarette rate of release and specific extinction area all apparent simultaneously
It reduces.
2nd, the present invention selects phosphorous-containing polyester polyalcohol and melamine polyalcohol to arrange in pairs or groups.It is formed using phosphorus, nitrogen as main ignition-proof element,
Its system itself has good synergistic effect, and surface can form one layer of dense foam layer of charcoal when heated, play heat-insulated, oxygen barrier,
Suppression cigarette prevents the effects that molten drop；And nitrogen P elements are introduced on polyurethane foam skeleton, nitrogen phosphorus ignition-proof element is avoided to migrate,
Permanent fire retardant is formed, reaches and uses no or little outer addition fire retardant, reduces harmful effect of the fire retardant to polyurethane foam performance,
Realize high compressive strength density ratio and hyperoxia exponential density ratio.
3rd, the present invention will be introduced into hard-foam polyurethane foam in the common smoke inhibition fire retardant FR808 in epoxy resin field and replace
Fire retardants, the flame retardant properties and smoke suppressing of foam such as TCPP, TEP, TCEP, DEEP of generation routine are further improved；
Smoke density grade can further be reduced.
4th, the present invention uses high NC0 index designs, by excessive NCO by the inductive formation PIR structures of catalyst, and it is close
Amine rigid heterocyclic structure and rigid benzene ring structure realize good dimensional stability together, reach high compressive strength density
Than.
5th, the present invention is using the non-hydrolytic silicon-carbon class surfactant for forming minimum abscess and the non-silicon of formation polar circle abscess
Class surfactant reduces the thermal conductivity factor of foam, improves the anisotropy and compressive strength of foam.
6th, the present invention is by melamine polyalcohol, phosphorous-containing polyester polyalcohol, smoke inhibition fire retardant, foaming agent, foam stabilizer, catalyst
Effectively collocation is prepared for a kind of to meet high compression-strength density ratio, hyperoxia the exponential density poly- ammonia led lower than, low cigarette simultaneously
Ester foamed material.
Specific embodiment
Technical scheme of the present invention is described in detail with reference to embodiments, it should be noted that be only below
The preferred embodiment of the present invention, for those of ordinary skill in the art, before the invention design is not departed from
It puts, various modifications and improvements can be made, these should belong to protection scope of the present invention.
Air LK443, air LK221 represent the non-silicon class surface of corresponding Air Prod ＆ Chem's production in the present invention
The model of activating agent；Similarly, it wins wound B8462 and represents that the silicon class surface of Evonik Degussa's production is lived
The model of property agent；Mei Side AK-8805 represent the foam stabilizer of the model AK-8805 of dolantin Shi Chuan Chemical Co., Ltd.s production.
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
30 parts~70 parts of alcohol, 30 parts~70 parts of phosphorous-containing polyester dihydric alcohol, 10 parts~20 parts of smoke inhibition fire retardant, physical blowing agent 10 parts~25
Part, 1 part~3 parts of foam stabilizer, 1 part~2 parts of chemical foaming agent and 2 parts~5 parts of catalyst.
Further, the component A includes the component of following parts by weight：36 parts of melamine polyalcohol, phosphorous-containing polyester binary
3.5 parts of 50 parts of alcohol, 13 parts of smoke inhibition fire retardant, 13 parts of physical blowing agent, 2 parts of foam stabilizer, 1.3 parts of chemical foaming agent and catalyst.
Further, the melamine polyalcohol is the polyalcohol that the polynary melamine of class is initiator, hydroxyl value 210 ±
10mgKOH/g, 6000 ± 1000mPas/25 DEG C of viscosity, acid value≤1.0mgKOH/g；The phosphorous-containing polyester dihydric alcohol be containing
Phosphorus aromatic diols, the phosphorous aromatic diols hydroxyl value are 190-200mgKOH/g, viscosity 2000-3500MPas/25
DEG C, acid value≤1mgKOH/g；Or the melamine polyalcohol is Jiangsu Chang Neng groups EDS-5083L；The phosphorous-containing polyester two
First alcohol is Beijing dolantin section innovative material DM2013.
Further, the smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；The even bubble
Agent for air LK443, air LK221, dolantin AK-8805 and win wound B8462 in it is one or more；The chemical foaming agent
For deionized water；The catalyst is two in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
Kind or more.
A kind of hard polyurethane foam based on polyurethane composition polyethers, including component A and component B；The component B is more
Polymethylene polyphenyl polyisocyanates；The weight ratio of the component A and component B is component A：Component B=1:1.0~1.7.
Preferably, the weight ratio of the component A and component B is component A：Component B=1:1.2~1.7.
Preferably, the weight ratio of the component A and component B is component A：Component B=1:1.4~1.6.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A is 20~25 DEG C, and the time stirred in advance is 10min, is stirred for
Time is 0.5h~1h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
Specific preparation method is as follows：
Step is as follows:
(1) by 30-70 parts of melamine polyalcohols, 70-30 parts of phosphorous-containing polyester dihydric alcohols, 10-20 parts of smoke inhibition fire retardants, 1-3 parts
Foam stabilizer, 1-2 part chemical foaming agent and 2-5 parts of catalyst are sequentially added in reaction kettle, are stirred in advance under the conditions of 20-25 DEG C 10 minutes
Component A is made in blowing after again plus stirring 0.5-1h such as 10-20 parts of physical blowing agents；
(2) using poly methylene poly phenyl poly isocyanate as component B, by the component A of step (1) and component B by
Mixing apparatus is known, according to weight ratio 1：It is prepared by 1-2 intervals or continuous or spraying.The specific embodiment of the invention is preferable over weight ratio
1：1.4-1.7, particularly preferred weight ratio 1：1.6 is continuously shaped by the double crawler belts of high-pressure foam agent machine mixed foaming.
For the present invention, the rigid foam prepared by the present invention is preferably according to GB/T6343-1995 to froth appearance
The preferred 30-50kg/m of core density3, particularly preferred 30-40kg/m3。
For the present invention, the rigid foam prepared by the present invention is preferably compressed according to GB/T8813-2008 to 10%
The compression stress of preferably greater than or equal to 150kPa, especially preferred greater than or equal to 180kPa or the foam of compressive strength.
For the present invention, the rigid foam prepared by the present invention preferably refers to foam oxygen according to GB/T2406-2009
Number preferably greater than 26, especially preferred more than 30 foam.
For the present invention, it is tested according to GB/T8625-2005, the hard polyurethane foams prepared by the present invention are averaged
Flue-gas temperature is less than 200 DEG C, and average combustion residue is more than 150mm.
For the present invention, it is tested according to GB/T8626-2007, is its fire by hard polyurethane foams prepared by the present invention
Flame height is the foam no more than 15cm.
For the present invention, it is tested according to GB/T8627-2007, the cigarette of hard polyurethane foams prepared by the present invention is close
It spends grade and is less than 75.
For the present invention, it is tested according to GB/T8626, when meeting igniting by hard polyurethane foams prepared by the present invention
Between=30s, 60s in ignite filter paper without density flaming droplet in Fs≤150mm and 60s.
For the present invention, (SBI) is tested according to GB/T20284, is met by hard polyurethane foams prepared by the present invention
FIGRA≤250W/s, LFS ＜ samples edge, THR600s≤15MJ.
For the present invention, the hard polyurethane foams prepared by the present invention meet above-mentioned examination criteria and are classified as B1
Grade nonflammable material.
Embodiment 1
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
30 parts of alcohol, 30 parts of phosphorous-containing polyester dihydric alcohol, 10 parts of smoke inhibition fire retardant, 10 parts of physical blowing agent, 1 part of foam stabilizer, chemical foaming agent 1
2 parts of part and catalyst；
Melamine polyalcohol is the polyalcohol that the polynary melamine of class is initiator, 210 ± 10mgKOH/g of hydroxyl value, viscosity
6000 ± 1000mPas/25 DEG C, acid value≤1.0mgKOH/g；
The phosphorous-containing polyester dihydric alcohol is phosphorous aromatic diols, and the phosphorous aromatic diols hydroxyl value is 190-
200mgKOH/g, viscosity are 2000-3500MPas/25 DEG C, acid value≤1mgKOH/g；
The smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；
The foam stabilizer for air LK443, air LK221, dolantin AK-8805 and win wound B8462 in it is one or more；
The chemical foaming agent is deionized water；
The catalyst is two kinds in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
Above combination.
Embodiment 2
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
70 parts of alcohol, 70 parts of phosphorous-containing polyester dihydric alcohol, 20 parts of smoke inhibition fire retardant, 20 parts of physical blowing agent, 3 parts of foam stabilizer, chemical foaming agent 2
5 parts of part and catalyst；
Melamine polyalcohol is the polyalcohol that the polynary melamine of class is initiator, 210 ± 10mgKOH/g of hydroxyl value, viscosity
6000 ± 1000mPas/25 DEG C, acid value≤1.0mgKOH/g；
The phosphorous-containing polyester dihydric alcohol is phosphorous aromatic diols, and the phosphorous aromatic diols hydroxyl value is 190-
200mgKOH/g, viscosity are 2000-3500MPas/25 DEG C, acid value≤1mgKOH/g；
The smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；
The foam stabilizer for air LK443, air LK221, dolantin AK-8805 and win wound B8462 in it is one or more；
The chemical foaming agent is deionized water；
The catalyst is two kinds in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
More than.
Embodiment 3
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
36 parts of alcohol, 50 parts of phosphorous-containing polyester dihydric alcohol, 13 parts of smoke inhibition fire retardant, 13 parts of physical blowing agent, 2 parts of foam stabilizer, chemical foaming agent
1.3 parts and 3.5 parts of catalyst；
Melamine polyalcohol is the polyalcohol that the polynary melamine of class is initiator, 210 ± 10mgKOH/g of hydroxyl value, viscosity
6000 ± 1000mPas/25 DEG C, acid value≤1.0mgKOH/g；
The phosphorous-containing polyester dihydric alcohol is phosphorous aromatic diols, and the phosphorous aromatic diols hydroxyl value is 190-
200mgKOH/g, viscosity are 2000-3500MPas/25 DEG C, acid value≤1mgKOH/g；
The smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；
The foam stabilizer for air LK443, air LK221, dolantin AK-8805 and win wound B8462 in it is one or more；
The chemical foaming agent is deionized water；
The catalyst is two kinds in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
More than.
Embodiment 4
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
45 parts of alcohol, 55 parts of phosphorous-containing polyester dihydric alcohol, 13 parts of smoke inhibition fire retardant, 15 parts of physical blowing agent, 2 parts of foam stabilizer, chemical foaming agent
1.7 parts and 3.5 parts of catalyst；
The melamine polyalcohol is Jiangsu Chang Neng groups EDS-5083L；
The phosphorous-containing polyester dihydric alcohol is Beijing dolantin section innovative material DM2013；
The smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；
The foam stabilizer for air LK443, air LK221, dolantin AK-8805 and win wound B8462 in it is one or more；
The chemical foaming agent is deionized water；
The catalyst is two kinds in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
More than.
Embodiment 5
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
36 parts of alcohol, 50 parts of phosphorous-containing polyester dihydric alcohol, 13 parts of smoke inhibition fire retardant, 13 parts of physical blowing agent, 2 parts of foam stabilizer, chemical foaming agent
1.3 parts and 3.5 parts of catalyst；
The melamine polyalcohol is Jiangsu Chang Neng groups EDS-5083L；
The phosphorous-containing polyester dihydric alcohol is Beijing section innovative material DM2013；
The smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；
The foam stabilizer for air LK443, air LK221, dolantin AK-8805 and win wound B8462 in it is one or more；
The chemical foaming agent is deionized water；
The catalyst is two kinds in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
More than.
Embodiment 6
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
60 parts of alcohol, 58 parts of phosphorous-containing polyester dihydric alcohol, 16 parts of smoke inhibition fire retardant, 16 parts of physical blowing agent, 2.8 parts of foam stabilizer, chemical blowing
4 parts of 1.8 parts of agent and catalyst.
The melamine polyalcohol is Jiangsu Chang Neng groups EDS-5083L；
The phosphorous-containing polyester dihydric alcohol is Beijing dolantin section innovative material DM2013；
The smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；
The physical blowing agent is the one or more of HCFC141B, HFC-134a, HFC-245fa, HFO-1233zd；
The foam stabilizer for air LK443, air LK221, dolantin AK-8805 and win wound B8462 in it is one or more；
The chemical foaming agent is deionized water；
The catalyst is two kinds in PC-5, PC-9, PC-41, PC-77, PT-303, PT-304, K-15, JXP-508
More than.
Embodiment 7
A kind of hard polyurethane foam based on polyurethane composition polyethers, including component A and component B；The component B is more
Polymethylene polyphenyl polyisocyanates；The weight ratio of the component A and component B is component A：Component B=1:1.0.
The composition of component A is using the component A of any one in embodiment 1-6.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A be 20 DEG C, the time stirred in advance be 10min, the time being stirred for
For 0.5h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
Embodiment 8
A kind of hard polyurethane foam based on polyurethane composition polyethers, including component A and component B；The component B is more
Polymethylene polyphenyl polyisocyanates；The weight ratio of the component A and component B is component A：Component B=1:1.2.
The composition of component A is using the component A of any one in embodiment 1-6.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A be 25 DEG C, the time stirred in advance be 10min, the time being stirred for
For 1h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A be 22 DEG C, the time stirred in advance be 10min, the time being stirred for
For 0.6h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
Embodiment 9
A kind of hard polyurethane foam based on polyurethane composition polyethers, including component A and component B；The component B is more
Polymethylene polyphenyl polyisocyanates；The weight ratio of the component A and component B is component A：Component B=1:1.4.
The composition of component A is using the component A of any one in embodiment 1-6.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A be 25 DEG C, the time stirred in advance be 10min, the time being stirred for
For 1h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
Embodiment 10
A kind of hard polyurethane foam based on polyurethane composition polyethers, including component A and component B；The component B is more
Polymethylene polyphenyl polyisocyanates；The weight ratio of the component A and component B is component A：Component B=1:1.7.
Component A uses the component A of any one in embodiment 1-6.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A be 25 DEG C, the time stirred in advance be 10min, the time being stirred for
For 0.5h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
Embodiment 11
A kind of polyurethane composition polyethers, including component A；The component A includes the component of following parts by weight：Melamine is polynary
60 parts of alcohol, 40 parts of phosphorous-containing polyester dihydric alcohol, 20 parts of smoke inhibition fire retardant, 25 parts of physical blowing agent, 3 parts of foam stabilizer, chemical foaming agent 1
4 parts of part and catalyst.
The melamine polyalcohol is Jiangsu Chang Neng groups EDS-5083L；EDS-5083L：60 parts；
The phosphorous-containing polyester dihydric alcohol is Beijing dolantin section innovative material DM2003；DM2013：40 parts；
The smoke inhibition fire retardant is FR808, and FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；FR808：20
Part；
The physical blowing agent is HCFC-141B, HCFC-141B：25 parts；
Foam stabilizer is the mixture of air LK443 and AK8805, and air LK443 and AK8805 are respectively 1.5 parts；
The chemical foaming agent be deionized water, deionized water：1 part；
The catalyst is the mixture of PC-5, PC-9, PC-41, K15 and JXP-508, specifically, PC-5：0.3 part,
PC-9：0.7 part, PC-41：1 part, K15：0.7 part and JXP-508：1.3 part.
A kind of hard polyurethane foam based on polyurethane composition polyethers, including component A and component B；The component B is more
Polymethylene polyphenyl polyisocyanates；The weight ratio of the component A and component B is component A：Component B=1:1.6.
A kind of preparation method of hard polyurethane foam, including step：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, change
It learns foaming agent and catalyst is added in reaction kettle, it is pre- to stir, physical blowing agent is then added in, polyurethane composition is made after being stirred for
Polyethers；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made polyurethane
Rigid foam.
Further, the temperature of the pre- stirring in step A be 22 DEG C, the time stirred in advance be 10min, the time being stirred for
For 0.7h；Forming operation is continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming in the step B.
Embodiment 12
The difference lies in the physical blowing agent is HCFC-141B, HCFC- to the present embodiment with embodiment 11
141B：35 parts, rest part is identical with embodiment 11.
Embodiment 13
The difference lies in the melamine polyalcohol is Jiangsu Chang Neng groups EDS- to the present embodiment with embodiment 11
5083L；EDS-5083L：40 parts；The phosphorous-containing polyester dihydric alcohol is Beijing dolantin section innovative material DM2013；DM2013：60
Part；Rest part is identical with embodiment 11.
Embodiment 14
The difference lies in the physical blowing agent is HCFC-141B, HCFC- to the present embodiment with embodiment 13
141B：35 parts, rest part is identical with embodiment 13.
Comparative example 1
The difference lies in 40 parts of 60 parts of melamine polyalcohol and phosphorous-containing polyester dihydric alcohol replace this comparative example with embodiment 11
It is changed to the big sucrose polyether polyol SU-450L in blue star east commonly used in the art：60 parts；The phthalic anhydride polyester binary of Si Taipan
Alcohol PS-3152：40 parts；FR808：20 parts with fire retardant TCPP：20 parts replace rest part identical with embodiment 11.
Comparative example 2
The difference lies in the physical blowing agent is HCFC-141B, HCFC- to this comparative example with comparative example 1
141B：35 parts, rest part is identical with comparative example 1.
Contrast test
Following tables 1 is made with the component for respectively participating in reacting of comparative example 1 and 2 in embodiment 11-14.
The each component contrast table of 1 embodiment 11-14 of table, comparative example 1 and comparative example 2
| Raw material model | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 1 | Comparative example 2 |
| EDS-5083L | 60 | 60 | 40 | 40 | 0 | 0 |
| DM2013 | 40 | 40 | 60 | 60 | 0 | 0 |
| SU-450L | 0 | 0 | 0 | 0 | 60 | 60 |
| PS-3152 | 0 | 0 | 0 | 0 | 40 | 40 |
| HCFC-141B | 25 | 35 | 25 | 35 | 25 | 35 |
| FR808 | 20 | 20 | 20 | 20 | 0 | 0 |
| TCPP | 0 | 0 | 0 | 0 | 20 | 20 |
| AK8805 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| LK443 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| PC5 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| PC9 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| PC41 | 1 | 1 | 1 | 1 | 1 | 1 |
| JXP508 | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 |
| K15 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| H2O | 1 | 1 | 1 | 1 | 1 | 1 |
According to the parts by weight ratio of each component in table 1, A, B component material are pressed into A：B=1：1.6 weight ratios pass through high pressure
Casting machine is uniformly mixed, and is injected mold, is cured through overmolding, and product is made, analyzes each performance indicator, obtains the following table 2.
2 performance comparison table of table
By upper table 2 it is found that the polyurethane foam of the embodiment of the present invention has compared with the polyurethane foam of comparative example routine
More excellent compressive strength density ratio, higher oxygen index (OI) density ratio and lower smoke density, so as to which the present invention has high pressure
Contracting strength to density ratio, hyperoxia exponential density ratio, low cigarette, low the characteristics of leading.
Technical scheme of the present invention can preferably be realized according to the record of this specification.
Claims (9)
1. a kind of polyurethane composition polyethers, which is characterized in that including component A；The component A includes the group of following parts by weight
Point：30 parts~70 parts of melamine polyalcohol, 30 parts~70 parts of phosphorous-containing polyester dihydric alcohol, 10 parts~20 parts of smoke inhibition fire retardant, physics hair
2 parts~5 parts of 10 parts~25 parts of infusion, 1 part~3 parts of foam stabilizer, 1 part~2 parts of chemical foaming agent and catalyst.
2. polyurethane composition polyethers according to claim 1, which is characterized in that the component A includes following parts by weight
Component：36 parts of melamine polyalcohol, 50 parts of phosphorous-containing polyester dihydric alcohol, 13 parts of smoke inhibition fire retardant, 13 parts of physical blowing agent, foam stabilizer
3.5 parts of 2 parts, 1.3 parts of chemical foaming agent and catalyst.
3. polyurethane composition polyethers according to claim 2, which is characterized in that the melamine polyalcohol is class polynary three
Polyalcohol of the poly cyanamid for initiator, 210 ± 10mgKOH/g of hydroxyl value, 6000 ± 1000mPas/25 DEG C of viscosity, acid value≤
1.0mgKOH/g；The phosphorous-containing polyester dihydric alcohol is phosphorous aromatic diols, and the phosphorous aromatic diols hydroxyl value is 190-
200mgKOH/g, viscosity are 2000-3500MPas/25 DEG C, acid value≤1mgKOH/g；Or the melamine polyalcohol is Jiangsu
Chang Neng groups EDS-5083L；The phosphorous-containing polyester dihydric alcohol is the DM2013 of Beijing dolantin section innovative material.
4. polyurethane composition polyethers according to claim 3, which is characterized in that the smoke inhibition fire retardant is FR808,
FR808 is Qingdao Lian Mei Chemical Co., Ltd. commercial product；The physical blowing agent is HCFC141B, HFC-134a, HFC-
245fa, HFO-1233zd's is one or more；The foam stabilizer is air LK443, air LK221, dolantin AK-8805 and win
It creates one or more in B8462；The chemical foaming agent is deionized water；The catalyst for PC-5, PC-9, PC-41,
It is two or more in PC-77, PT-303, PT-304, K-15, JXP-508.
5. a kind of hard polyurethane foam of the polyurethane composition polyethers based on described in claim 1-4 any one, feature
It is, including component A and component B；The component B is poly methylene poly phenyl poly isocyanate；The component A's and component B
Weight ratio is component A：Component B=1:1.0~1.7.
6. hard polyurethane foam according to claim 5, which is characterized in that the weight ratio of the component A and component B
For component A：Component B=1:1.2~1.7.
7. hard polyurethane foam according to claim 6, which is characterized in that the weight ratio of the component A and component B
For component A：Component B=1:1.4~1.6.
8. the preparation method of the hard polyurethane foam described in a kind of claim 6-7 any one, which is characterized in that including step
Suddenly：
A, polyurethane composition polyethers is prepared：By melamine polyalcohol, phosphorous-containing polyester dihydric alcohol, smoke inhibition fire retardant, foam stabilizer, chemistry hair
Infusion and catalyst are added in reaction kettle, pre- to stir, and then add in physical blowing agent, and polyurethane composition is made after being stirred for and gathers
Ether；
B, hard polyurethane foam is prepared：Component B is uniformly mixed with polyurethane composition polyethers, be molded after be made rigid poly urethanes
Foam.
9. the preparation method of hard polyurethane foam according to claim 8, which is characterized in that the pre- stirring in step A
Temperature for 20~25 DEG C, the time stirred in advance is 10min, and the time being stirred for is 0.5h~1h；Behaviour is molded in the step B
Make continuously shaped using the double crawler belts of high-pressure foam agent machine mixed foaming.
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| CN117327251A (en) * | 2023-12-01 | 2024-01-02 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
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| CN117327251A (en) * | 2023-12-01 | 2024-01-02 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
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| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Youming Inventor after: Chen Junxin Inventor after: Hou Debo Inventor after: Zhen Cheng Inventor before: Li Youming Inventor before: Chen Junxin Inventor before: Hou Debo Inventor before: Zeng Cheng |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180710 |