CN1295266C - Preparation method of fire retardant high activity polymer polyether polyol and method for preparing high elastic resilience fire retardant golyurethane soft foam material therefrom - Google Patents
Preparation method of fire retardant high activity polymer polyether polyol and method for preparing high elastic resilience fire retardant golyurethane soft foam material therefrom Download PDFInfo
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- CN1295266C CN1295266C CNB2004100358963A CN200410035896A CN1295266C CN 1295266 C CN1295266 C CN 1295266C CN B2004100358963 A CNB2004100358963 A CN B2004100358963A CN 200410035896 A CN200410035896 A CN 200410035896A CN 1295266 C CN1295266 C CN 1295266C
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Abstract
The present invention relates to a polyether polyhydric alcohol of a fire retardant highly active polymer, and a preparation method of the polyether polyhydric alcohol for a high resilience fire retardant polyurethane soft bubble. Universal highly active polyether polyhydric alcohol is used as a continuous phase, and a subnanometer ultramicro polymer particle of the amidocyanogen diisocyanate modified polyether polyhydric alcohol (a dispersing agent) of a surface grafting part is used as a dispersed phase, and a stable polymer colloidal dispersed system comprising the continuous phase and the dispersed phase forms the polyether polyhydric alcohol of the polyether polyhydric alcohol of a fire retardant highly active polymer. Formaldehyde, urea, melamine and hexamethylenetetramine are used by the preparation method to react for 0.5 to 4 hours in highly active polyether polyhydric alcohol at 65 DEG C and 98 DEG C under the existence of the dispersing agent, and the polyether polyhydric alcohol of a fire retardant highly active polymer is prepared by drying. The polyether polyhydric alcohol of a fire retardant highly active polymer does not contain the toxic and harmful substances of phosphorus, halogen, styrene, acrylonitrile, and the like, and has the characteristics of simple preparation process, low cost, easy foaming, etc. The prepared polyether polyhydric alcohol of a fire retardant highly active polymer, and a diisocyanate compound are prepared into fire retardant high resilience polyurethane foam by cold moulding and free foaming technology under the existence of a trialkylamine catalyst, an organic metallic catalyst, water, a crosslinking agent and a silicon oil foam stabilizer. The material of the fire retardant high resilience polyurethane foam high fire retardance (an oxygen value number can reach 28%).
Description
Technical field
The invention belongs to polyether polyol and preparation Application Areas thereof, be specifically related to a kind of fire-retardant highly reactive polymer polyether glycol preparation method and and be used to prepare the method for the soft foam material of high resilience flame retardant polyurethane.
Background technology
Polyurethane foamed material is a kind of superpolymer with special performance and many-sided purposes.It is a basic raw material with polyether glycol and diisocyanate, allocate less water, organic silicon surfactant, whipping agent into, under the acting in conjunction of organotin and tertiary amine catalyst, form, can make hard, semi-rigid and flexible urethane foam with it, be applied to the aspects such as saddle of cushion, back cushion, inside gadget and the motorcycle of vehicle mainly as cushioning material, also can be used for making simultaneously the products for civilian use such as sofa, mattress, finishing material.
Polyether polyol normally vinyl monomer in the presence of dispersion agent in polyether glycol the diffuse-aggregate product of free radical, the used vinyl monomer of polyether polyol at the beginning of the seventies is a vinyl cyanide, its solid content (polymer content) is 5%～25%, viscosity height, look Huang, easily makes the heartburn variable color of polyurethane foam; The mid-80 prepares polyether polyol with vinyl cyanide and vinylbenzene mix monomer, and its solid content is 20%～30%, and styrene content is more than 50%; At the initial stage nineties, abroad some companies release one after another solid content more than 40%, and viscosity is lower than the polyether polyol of 5500mPas (25 ℃), as European patent Eur.Pat.Ep778,301; PCT.Int.Appl.Wo.97,15,605; PCT.Int.Appl.Wo.97,15,606 disclosed polyether polyols, but these polyether polyols all do not have flame retardant resistance, do not have flame retardant resistance with its prepared polyurethane foam yet.
The urethane foam goods very easily burn, fire-retardant difficulty, and flame resistant method commonly used at present is to add fire retardant in the raw material of producing urethane mostly, used fire retardant mainly contains reaction-type flame-retarding polyether glycol and non-response type small molecules fire retardant; The reaction-type flame-retarding polyether glycol mainly is phosphorous chlorine polyether glycol, and is low with the prepared polyurethane foam cost of this polyether glycol height, bearing capacity; The kind of non-response type small molecules fire retardant mainly contains Sb
2O
3, liquid or solid compounds such as melamine class, phosphorous acid ester and chloride-based, use the non-reacted fire retardant of liquid, volatilize gradually with the use fire retardant of foam materials, flame retardant effect descends, and environment is caused certain harm; Use the non-reactive flame retardant of solid can obviously increase the viscosity of polyether glycol, increase the foam process difficulty, reduce the percentage of open area of foams, and make the density of foams uneven up and down.This based flame retardant uses trouble, and difficulty mixes, large usage quantity, fire-retardant cost height.
United States Patent (USP) 4,214,055,3,953,393 use the fire resistant polymer polylol of two or more mix monomer copolymerization in vinylchlorid, vinylidene chloride, vinylbenzene, the vinyl cyanide, and prepare resistance combustion polyurethane foam with it.But the homopolymer of vinylchlorid, vinylidene chloride and copolymerization are normally heat-labile, emit deleterious HCl gas in foaming process, and foaming machine is had corrodibility; Japanese Patent Jpn.Kokai.Tokyo.JP.0959, the employed fire-retardant thing of 341 disclosed fire resistant polymer polylols is a polyvinyl chloride, equally also is heat-labile; United States Patent (USP) U.S.5,250,581 disclose with tribromo-benzene ethene and vinyl cyanide mix monomer copolymerization polymer polyatomic alcohol, have certain flame retardant resistance with the prepared urethane foam of this polymer polyatomic alcohol, but tribromo-benzene ethene synthesizes difficulty, price is high, is difficult to obtain.
Summary of the invention
One of purpose of the present invention is to provide a kind of preparation method of fire-retardant highly reactive polymer polyether glycol, it is different from free radical dispersion polymerization traditionally, but condensation dispersion polymerization, with the prepared fire-retardant highly reactive polymer polyether glycol of this method, have active high, hazardous and noxious substances such as dispersed phase polymer particle diameter little (0.1 micron～0.5 micron), not phosphorous, halogen, vinylbenzene and vinyl cyanide, environmental protection, and have that preparation technology is simple, cost is low, be easy to characteristics such as foaming.
Two of purpose of the present invention is to provide a kind of flame-retardant high-resilience urethane cold molding foaming method, with the prepared high resilience resistance combustion polyurethane foam of this method, have the reinforcement of inferior nano-dispersed gathering compound ultramicron, fire-retardant characteristic, so this polyurethane foamed material has higher flame retardant resistance (the oxygen value number can reach 28%) and than high resilience with press and fall into hardness.
Fire-retardant highly reactive polymer polyether glycol of the present invention is that the polymeric colloid dispersion system that inferior nanometer polymer ultramicron is a disperse phase, two-phase constituted of the aminated vulcabond modified polyether polylol of external phase, surface grafting part (dispersion agent) is formed by general polyether polyol with high activity.
The general polyether polyol with high activity of above-mentioned external phase is propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, the functionality of its polyvalent alcohol is between 2～4, hydroxyl value is between 19mgKOH/g～36mgKOH/g, proportion of primary OH groups is between 65%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination.
Above-mentioned inferior nanometer polymer ultramicron disperse phase be median size at 0.1 micron～0.5 micron, " hair " polymer microballoon of the polyether glycol of the aminated vulcabond modification of surface grafting part.
Above-mentioned external phase is 98: 2～30: 70 with the ratio of the quality of disperse phase.
Its ethoxylated polyhydric alcohol is meant propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms in the aminated vulcabond modified polyether polylol of above-mentioned part, its polyvalent alcohol functionality is between 2～4, hydroxyl value is between 19mgKOH/g～38mgHO/g, proportion of primary OH groups is between 5%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination; Its vulcabond is a kind of in tolylene diisocyanate, the '-diphenylmethane diisocyanate or the mixture of the two; It is aminated to be the reaction of diamine and vulcabond.
Above-mentioned polymer microballoon is formaldehyde and urea, trimeric cyanamide, hexamethylenetetramine polycondensate.
Flame-retardant high-resilience ammonia ester foam of the present invention be with fire-retardant highly reactive polymer polyether glycol of the present invention, general polyether polyol with high activity and diisocyanate cpd tertiary amine, organo-metallic catalyst, water, pneumatogen and a small amount of silicone oil foam stabilizer down, foam and free technology makes through cold molding.
Above-mentioned diisocyanate cpd is a kind of in tolylene diisocyanate (T80/20), the '-diphenylmethane diisocyanate (PAPI) or the mixture of the two, the two blending ratio of tolylene diisocyanate (T80/20), '-diphenylmethane diisocyanate (PAPI) was at 50: 50～100: 0, tolylene diisocyanate (T80/20) preferably, and reduce the flame retardant resistance that makes resistance combustion polyurethane foam with diisocyanate index and improve.
Above-mentioned block foam process is cold molding foaming and free foaming technique.
The manufacture method of fire-retardant highly reactive polymer polyether glycol of the present invention is as follows:
Respectively with external phase-general polyether polyol with high activity, the aminated vulcabond modified polyether polylol of dispersion agent-part, nitrogen containing monomer-urea, trimeric cyanamide, contain aldehyde monomer-formaldehyde, and condensation reaction promotor joins in the closed reactor that has agitator, temperature regulator meter, make temperature rise to setting-up point, behind this temperature isothermal reaction certain hour, vacuum-drying removes volatile components, add general polyether polyol with high activity, obtain fire-retardant highly reactive polymer polyether glycol.
Above-mentioned general polyether polyol with high activity and the general polyether polyol with high activity of adding are propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, the functionality of its polyvalent alcohol is between 2～4, hydroxyl value is between 19mgKOH/g～38mgKOH/g, proportion of primary OH groups is between 65%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination; The consumption of the general polyether polyol with high activity that adds is 100%～9000% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum, is preferably 150%～2000%; The general polyether polyol with high activity that adds is 100: 0～100: 1000 with the ratio of the quality of the general polyether polyol with high activity of adding.
Above-mentioned formaldehyde is concentration at 25%～45% formaldehyde, and preferably concentration is at 37% formaldehyde, and its consumption (in 37% concentration of formaldehyde) is 40%～400% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum, is preferably 50%～200%.
Above-mentioned nitrogen containing monomer is urea, trimeric cyanamide, and the ratio of the quality of its urea, trimeric cyanamide was preferably 100: 50 between 0: 100～100: 0; Nitrogen containing monomer consumption-urea, trimeric cyanamide quality sum be except that the general polyether polyol with high activity of adding the whole reaction system quality 2%～60%, be preferably 10%～48%.
Above-mentioned condensation reaction promotor is hexamethylenetetramine, tosic acid, ammoniacal liquor, formic acid etc., is preferably hexamethylenetetramine, and its hexamethylenetetramine consumption is 0.07%～20% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum.
Above-mentioned temperature of reaction is a setting-up point, generally at 50 ℃～100 ℃, is preferably 65 ℃～95 ℃, preferably 75 ℃～85 ℃.
The above-mentioned reaction times is at 0.5～6 hour, is preferably at 1～5 hour preferably 2～4 hours.
Above-mentioned vacuum-drying is meant at a certain temperature, generally at 35 ℃～100 ℃, is preferably 40 ℃～95 ℃; The vacuum-drying certain hour generally at 1～12 hour, is preferably at 2～10 hours.
The polyether glycol of the aminated vulcabond modification of above-mentioned dispersion agent-part plays the effect of dispersion agent in synthetic fire-retardant highly reactive polymer polyether glycol, its consumption is 0.5%～150% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum, is preferably 10%～80%.
The preparation method of the polyether glycol of the aminated vulcabond modification of above-mentioned part is as follows:
Under 35 ℃～45 ℃, respectively polyether glycol, vulcabond encapsulant, vulcabond and tertiary amine are joined in the closed reactor that has agitator, thermometer, make temperature rise to 75 ℃～85 ℃, in this temperature isothermal reaction after 4～6 hours, add diamine, be warming up to 110 ℃～125 ℃ again, reacted 0.5～3 hour.Obtain the aminated vulcabond modified polyether polylol of part.
Above-mentioned polyether glycol is meant propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, its polyvalent alcohol functionality is between 2～4, hydroxyl value is between 19mgKOH/g～38mgKOH/g, proportion of primary OH groups is between 5%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination.
Above-mentioned vulcabond encapsulant can be phenolic compound, beta-dicarbonyl compound, oxime compounds, is preferably oxime compounds, as methyl ethyl ketoxime.
Above-mentioned diisocyanate compound is a kind of in tolylene diisocyanate, the '-diphenylmethane diisocyanate or the mixture of the two, is preferably tolylene diisocyanate.
Above-mentioned tertiary amine is a kind of or mixture more than two kinds and two kinds in triethylamine, tripropyl amine, the Tributylamine, is preferably triethylamine.
Above-mentioned diamine is a kind of or mixture more than two kinds and two kinds in quadrol, propylene diamine, the butanediamine, is preferably quadrol.
The mol ratio of above-mentioned polyether glycol, tolylene diisocyanate, quadrol, triethylamine was at 3: 1: 1: 0.001～1: 1:: between 1: 0.08.
The method that is the fire-retardant foam material of feedstock production high-rebound polyurethane with fire-retardant highly reactive polymer polyether glycol of the present invention is as follows:
In mixing tank, respectively fire-retardant highly reactive polymer polyether glycol, polyether polyol with high activity, amine catalyst, delay amine catalyst, water, linking agent and silicone oil foam stabilizer are mixed the back and add diisocyanate cpd, high-speed mixing is injected mould or free foaming and is made resistance combustion polyurethane foam.
Above-mentioned silicone oil foam stabilizer is one or more silicone foam stabilizer, and its consumption (w/w) is 0.08%～1.3% of a polyether glycol, is preferably 0.2%～1.2%
Above-mentioned tertiary amine catalyst is triethylene diamine, triethylamine, N, N, N ', N '-tetramethyl--1,3, one or more tertiary amine catalysts in-butanediamine, N-Ethylmorphine quinoline, two (beta-dimethyl-amine ethyl) ether, the diisopropanolamine (DIPA) etc.
Above-mentioned diisocyanate cpd is a kind of in tolylene diisocyanate (T80/20), the '-diphenylmethane diisocyanate (PAPI) or the mixture of the two.The blending ratio tolylene diisocyanate (T80/20) of the two: '-diphenylmethane diisocyanate (PAPI) is at 100: 0～70: 30, preferably 80: 20.
Above-mentioned linking agent is one or more the mixture in glycerine, TriMethylolPropane(TMP), diethanolamine, the trolamine.Basic recipe is as follows:
Basic recipe is as follows:
The A component
Common polyether polyol with high activity: 0～70 part
Water: 1～3 part
Postpone amine catalyst: 0.1～0.3 part
Sanya ethylene diamine: 0.1～0.5 part
Silicone oil: 0.7～1.2 part
1～2.5 part of linking agent
The fire-retardant highly reactive polymer polyether glycol of the present invention: rest part
Add up to 100 parts
The B component
Diisocyanate index: 100～115
The present invention has the following advantages compared with prior art;
1. this flame-retardant polymer polyether glycol, hazardous and noxious substances such as not phosphorous, halogen, vinylbenzene and vinyl cyanide, and have that preparation technology is simple, cost is low, be easy to characteristics such as foaming.
2. Zhi Bei resistance combustion polyurethane foam has the reinforcement of inferior nano-dispersed gathering compound ultramicron, fire-retardant characteristic, so this polyurethane foamed material has higher flame retardant resistance (the oxygen value number can reach 28%) and higher mechanical property and presses and fall into hardness.
Description of drawings
Fig. 1 is synthetic, the foaming formulation and the flame-retardant high-resilience polyurethane foam performance synopsis of fire-retardant highly reactive polymer polyether glycol.
Annotate among the figure: dispersion agent I, pastern divide aminated vulcabond modified polyether polylol.
Performance A is the performance of fire-retardant highly reactive polymer polyether glycol.
Stability/the moon is that nature is deposited the non-setting time, month.
Performance B is a polyurathamc foamy performance.
The foaming basic recipe:
The A component
Common polyether polyol with high activity: 0 part
Water; 2 parts
Postpone amine catalyst (EPS102): 0.1 part
Sanya ethylene diamine (DABACO A331v): 0.3 part
Silicone oil (DC5365): 1.1 parts
1.5 parts of glycerine
The fire-retardant highly reactive polymer polyether glycol of the present invention: rest part
Add up to 100 parts
The B component
Toluene diisocyanate index: 102%
Embodiment
The raw material of the embodiment of the invention is as follows:
Polyether polyol with high activity N330: glycerine or TriMethylolPropane(TMP) are initiator, propylene oxide ring-opening polymerization, the 16% ethylene oxide-capped polyether glycol that forms, its polymerization process can adopt traditional anionoid polymerization technology and DMC catalysts polymerization technique or the two combination, hydroxyl value 34mgKOH/g～36mgKOH/g, proportion of primary OH groups is between 60%～85%.
Formaldehyde: the formalin of concentration 37%
The preparation of the polyether glycol of the aminated vulcabond modification of part:
Embodiment 1: under 40 ℃ with polyether glycol N330,960 kilograms, 17.4 kilograms of methyl ethyl ketoximes, 34.8 kilograms of tolylene diisocyanates and triethylamine, 0.12 kilogram joins in the closed reactor that has agitator, thermometer, make temperature rise to 80 ℃, after 5 hours, add quadrol, 12 kilograms in this temperature isothermal reaction, be warming up to 118 ℃ again, reacted 1 hour.Obtain the aminated vulcabond modified polyether polylol of part.
Embodiment 2: respectively with general polyether polyol with high activity N330,550 kilograms, the aminated vulcabond modified polyether polylol of part, 61 kilograms, 197 kilograms in formaldehyde, 123 kilograms in urea, 61 kilograms of trimeric cyanamides, 5 kilograms of hexamethylenetetramines, the water 120 kg, join and have agitator, in airtight 3000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, add polyether polyol with high activity N330,580 kilograms, obtain fire-retardant highly reactive polymer polyether glycol, see the synthetic of fire-retardant highly reactive polymer polyether glycol, foaming formulation and flame-retardant high-resilience polyurethane foam performance synopsis embodiment 2.
Embodiment 3: respectively with general polyether polyol with high activity N330,550 kilograms, the aminated vulcabond modified polyether polylol of part, 61 kilograms, 197 kilograms in formaldehyde, 123 kilograms in urea, 61 kilograms of trimeric cyanamides, 5 kilograms of hexamethylenetetramines, the water 120 kg, join and have agitator, in airtight 3000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, add polyether polyol with high activity N330,380 kilograms, obtain fire-retardant highly reactive polymer polyether glycol, see the synthetic of fire-retardant highly reactive polymer polyether glycol, foaming formulation and flame-retardant high-resilience polyurethane foam performance synopsis embodiment 3.
Embodiment 4: respectively with general polyether polyol with high activity N330,550 kilograms, the aminated vulcabond modified polyether polylol of part, 61 kilograms, 197 kilograms in formaldehyde, 123 kilograms in urea, 61 kilograms of trimeric cyanamides, 5 kilograms of hexamethylenetetramines, the water 120 kg, join and have agitator, in airtight 3000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, add polyether polyol with high activity N330,180 kilograms, obtain fire-retardant highly reactive polymer polyether glycol, see the synthetic of fire-retardant highly reactive polymer polyether glycol, foaming formulation and flame-retardant high-resilience polyurethane foam performance synopsis embodiment 4.
Embodiment 5: respectively with general polyether polyol with high activity N330,550 kilograms, the aminated vulcabond modified polyether polylol of part, 51 kilograms, 197 kilograms in formaldehyde, 123 kilograms in urea, 61 kilograms of trimeric cyanamides, 5 kilograms of hexamethylenetetramines, the water 120 kg, join and have agitator, in airtight 3000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, add polyether polyol with high activity N330,580 kilograms, obtain fire-retardant highly reactive polymer polyether glycol, see the synthetic of fire-retardant highly reactive polymer polyether glycol, foaming formulation and flame-retardant high-resilience polyurethane foam performance synopsis embodiment 5.
Embodiment 6: respectively with general polyether polyol with high activity N330,550 kilograms, the aminated vulcabond modified polyether polylol of part, 41 kilograms, 197 kilograms in formaldehyde, 123 kilograms in urea, 61 kilograms of trimeric cyanamides, 5 kilograms of hexamethylenetetramines, the water 120 kg, join and have agitator, in airtight 3000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, add polyether polyol with high activity N330,580 kilograms, obtain fire-retardant highly reactive polymer polyether glycol, see the synthetic of fire-retardant highly reactive polymer polyether glycol, foaming formulation and flame-retardant high-resilience polyurethane foam performance synopsis embodiment 6.
Embodiment 7: respectively with general polyether polyol with high activity N330,550 kilograms, the aminated vulcabond modified polyether polylol of part, 31 kilograms, 197 kilograms in formaldehyde, 123 kilograms in urea, 61 kilograms of trimeric cyanamides, 5 kilograms of hexamethylenetetramines, the water 120 kg, join and have agitator, in airtight 3000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, add polyether polyol with high activity N330,580 kilograms, obtain fire-retardant highly reactive polymer polyether glycol, see the synthetic of fire-retardant highly reactive polymer polyether glycol, foaming formulation and flame-retardant high-resilience polyurethane foam performance synopsis embodiment 7.
Embodiment 8: respectively with general polyether polyol with high activity N330,550 kilograms, the aminated vulcabond modified polyether polylol of part, 21 kilograms, 197 kilograms in formaldehyde, 123 kilograms in urea, 61 kilograms of trimeric cyanamides, 5 kilograms of hexamethylenetetramines, the water 120 kg, join and have agitator, in airtight 3000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, add polyether polyol with high activity N330,580 kilograms, obtain fire-retardant highly reactive polymer polyether glycol, see the synthetic of fire-retardant highly reactive polymer polyether glycol, foaming formulation and flame-retardant high-resilience polyurethane foam performance synopsis embodiment 8.
Example 9 (comparison example): feed way is with example 1, feeding quantity is 0 kilogram except that the add-on of the aminated vulcabond modified polyether polylol of part I, other add-ons are with example 1, the polyether polyol that obtains, stability is bad, naturally deposit three days precipitations, see synthetic, the foaming formulation and the flame-retardant high-resilience polyurethane foam performance synopsis embodiment 9 of fire-retardant highly reactive polymer polyether glycol.
Claims (17)
1. fire-retardant highly reactive polymer polyether glycol preparation method, it is characterized in that it is an external phase by general polyether polyol with high activity, the inferior nanometer polymer ultramicron of the aminated vulcabond modified polyether polylol of surface grafting part is a disperse phase, the polymeric colloid dispersion system that two-phase constituted is formed, the general polyether polyol with high activity of external phase is the propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, the functionality of its polyvalent alcohol is between 2～4, hydroxyl value is between 19mgKOH/g～36mgKOH/g, proportion of primary OH groups is between 65%～98%, its polymerization process adopts traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, the particle diameter of dispersing phase of the inferior nanometer polymer ultramicron of the aminated vulcabond modified polyether polylol of surface grafting part is between 0.1 micron～0.5 micron, and external phase is 98: 2～30: 70 with the ratio of the quality of disperse phase.
2. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 1, it is characterized in that inferior nanometer polymer ultramicron is the polycondensate of formaldehyde and urea, trimeric cyanamide, hexamethylenetetramine.
3. one kind according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 1, it is characterized in that it is made up of following technology:
Respectively with external phase-general polyether polyol with high activity, the aminated vulcabond modified polyether polylol of dispersion agent-part, nitrogen containing monomer-urea, trimeric cyanamide, contain aldehyde monomer-formaldehyde, and condensation reaction promotor joins in the closed reactor that has agitator, temperature regulator meter, make temperature rise to 65 ℃～95 ℃ of setting-up point, in this temperature isothermal reaction after 2～4 hours; 92 ℃ of following vacuum-dryings 4 hours, remove volatile components, add general polyether polyol with high activity again, obtain fire-retardant highly reactive polymer polyether glycol.
4. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 3, it is characterized in that above-mentioned general polyether polyol with high activity and the general polyether polyol with high activity of adding are propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, the functionality of its polyvalent alcohol is between 2～4, hydroxyl value is between 19mgKOH/g～38mgKOH/g, proportion of primary OH groups is between 65%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination; The consumption of the general polyether polyol with high activity that adds is 100%～9000% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum, and the general polyether polyol with high activity of adding is 100: 0～100: 1000 with the ratio of the quality of the general polyether polyol with high activity of adding.
5. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 3, it is characterized in that above-mentioned formaldehyde is concentration at 25%～45% formaldehyde, its consumption is 40%～400% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum in 37% concentration of formaldehyde.
6. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 3, it is characterized in that above-mentioned nitrogen containing monomer is urea, trimeric cyanamide, the ratio of the quality of its urea, trimeric cyanamide between 0: 100～100: 0, nitrogen containing monomer consumption-urea, trimeric cyanamide quality sum be except that the general polyether polyol with high activity of adding the whole reaction system quality 2%～60%.
7. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 3, it is characterized in that above-mentioned condensation reaction promotor is hexamethylenetetramine, tosic acid, ammoniacal liquor, formic acid, its hexamethylenetetramine consumption is 0.07%～20% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum
8. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 3, it is characterized in that the polyether glycol of the aminated vulcabond modification of an above-mentioned dispersion agent part plays the effect of dispersion agent in synthetic fire-retardant highly reactive polymer polyether glycol, its consumption is 0.5%～150% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum.
9. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 3, the preparation method of polyether glycol who it is characterized in that the aminated vulcabond modification of a kind of part is as follows: under 35 ℃～45 ℃ respectively with polyether glycol, the vulcabond encapsulant, vulcabond and tertiary amine join and have agitator, in the closed reactor of thermometer, make temperature rise to 75 ℃～85 ℃, in this temperature isothermal reaction after 4～6 hours, add diamine, be warming up to 110 ℃～125 ℃ again, reacted 0.5～3 hour, and obtained the aminated vulcabond modified polyether polylol of part.
10. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 9, it is characterized in that polyether glycol is meant propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part, the ethylene oxide-capped polyether glycol that forms, its polyvalent alcohol functionality is between 2～4, hydroxyl value is between 19mgKOH/g～38mgKOH/g, proportion of primary OH groups is between 5%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination.
11., it is characterized in that the vulcabond encapsulant can be phenolic compound, beta-dicarbonyl compound, oxime compounds among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 9.
12., it is characterized in that diisocyanate compound among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part is a kind of in tolylene diisocyanate, the '-diphenylmethane diisocyanate or the mixture of the two according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 9.
13., it is characterized in that tertiary amine among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part is a kind of or mixture more than two kinds and two kinds in triethylamine, tripropyl amine, the Tributylamine according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 9.
14., it is characterized in that diamine among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part is a kind of or mixture more than two kinds and two kinds in quadrol, propylene diamine, the butanediamine according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 9.
15. according to the described fire-retardant highly reactive polymer polyether glycol preparation method of claim 9, the mol ratio that it is characterized in that polyether glycol, tolylene diisocyanate, quadrol, triethylamine among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part was at 3: 1: 1: 0.001～1: 1:: between 1: 0.08.
16. one kind is used to prepare the method for the fire-retardant soft foam material of high-rebound polyurethane according to claim 1 method, it is characterized in that it comprises following technology:
In mixing tank, respectively fire-retardant highly reactive polymer polyether glycol, polyether polyol with high activity, amine catalyst, delay amine catalyst, water, linking agent and silicone oil foam stabilizer are mixed the back and add diisocyanate cpd, high-speed mixing is injected mould or free foaming and is made resistance combustion polyurethane foam.
17. according to the described method for preparing the fire-retardant soft foam material of high-rebound polyurethane of claim 16, it is characterized in that above-mentioned diisocyanate cpd is a kind of among tolylene diisocyanate T80/20, the '-diphenylmethane diisocyanate PAPI or the mixture of the two, the blending ratio tolylene diisocyanate T80/20 of the two: '-diphenylmethane diisocyanate PAPI was at 100: 0～70: 30.
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| CNB2004100358963A CN1295266C (en) | 2004-09-30 | 2004-09-30 | Preparation method of fire retardant high activity polymer polyether polyol and method for preparing high elastic resilience fire retardant golyurethane soft foam material therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011081793A1 (en) * | 2009-12-29 | 2011-07-07 | Dow Global Technologies Inc. | Method for making low density polyurethane foam for sound and vibration absorption |
| CN102673450A (en) * | 2012-05-22 | 2012-09-19 | 昆山飞宇精密模具有限公司 | Automobile seat |
| CN104031235B (en) | 2013-03-05 | 2016-07-13 | 万华化学（北京）有限公司 | A kind of preparation method of visco-elasticity polyurethane sound-absorbing foam |
| CN103755950B (en) * | 2014-01-16 | 2016-03-02 | 南京红宝丽股份有限公司 | A kind of continuous production method of flame retardant polyether polyol |
| CN104877102A (en) * | 2015-06-03 | 2015-09-02 | 威海云山科技有限公司 | Flame-retardant rigid polyurethane foam heat insulation plate |
| CN105968307A (en) * | 2016-06-28 | 2016-09-28 | 苏州井上高分子新材料有限公司 | Polyurethane composition for automobile interior carpet |
| CN107540811B (en) * | 2017-08-08 | 2020-06-09 | 海泉风雷新能源发电股份有限公司 | Melamine graft modified polyurethane plastic and preparation method thereof |
| CN111154058B (en) * | 2020-01-03 | 2021-10-22 | 万华化学集团股份有限公司 | Flame-retardant polymer polyol and preparation method and application thereof |
| CN112851901A (en) * | 2021-01-08 | 2021-05-28 | 福建省天骄化学材料有限公司 | High-activity flame-retardant polymer polyol and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953393A (en) * | 1974-01-07 | 1976-04-27 | Basf Wyandotte Corporation | Low temperature process for the preparation of graft copolymer dispersions |
| US4214055A (en) * | 1978-11-17 | 1980-07-22 | Union Carbide Corporation | High resilience flame-retardant polyurethane foams based on polymer/polyol compositions |
| US5250581A (en) * | 1990-09-26 | 1993-10-05 | Arco Chemical Technology, L.P. | Polymer polyols containing halogenated aromatic monomers |
| JPH0959341A (en) * | 1995-08-24 | 1997-03-04 | Sanyo Chem Ind Ltd | Polymer polyol composition and production of frame-retardant polyurethane |
| WO1997015606A1 (en) * | 1995-10-23 | 1997-05-01 | The Dow Chemical Company | Polyurethane foam formulations having improved flowability and flexible polyurethane foams prepared therewith |
| US6068790A (en) * | 1995-12-07 | 2000-05-30 | Shell Oil Company | Polyol formulation for producing latex-like flexible polyurethane foam |
| CN1133682C (en) * | 1999-01-22 | 2004-01-07 | 山东建筑材料工业学院 | Fire resistant polymer polylol and its use |
| CN1143873C (en) * | 1998-09-10 | 2004-03-31 | 国际壳牌研究有限公司 | Co-initiated polyether polyol and process for its preparation |
-
2004
- 2004-09-30 CN CNB2004100358963A patent/CN1295266C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953393A (en) * | 1974-01-07 | 1976-04-27 | Basf Wyandotte Corporation | Low temperature process for the preparation of graft copolymer dispersions |
| US4214055A (en) * | 1978-11-17 | 1980-07-22 | Union Carbide Corporation | High resilience flame-retardant polyurethane foams based on polymer/polyol compositions |
| US5250581A (en) * | 1990-09-26 | 1993-10-05 | Arco Chemical Technology, L.P. | Polymer polyols containing halogenated aromatic monomers |
| JPH0959341A (en) * | 1995-08-24 | 1997-03-04 | Sanyo Chem Ind Ltd | Polymer polyol composition and production of frame-retardant polyurethane |
| WO1997015606A1 (en) * | 1995-10-23 | 1997-05-01 | The Dow Chemical Company | Polyurethane foam formulations having improved flowability and flexible polyurethane foams prepared therewith |
| US6068790A (en) * | 1995-12-07 | 2000-05-30 | Shell Oil Company | Polyol formulation for producing latex-like flexible polyurethane foam |
| CN1143873C (en) * | 1998-09-10 | 2004-03-31 | 国际壳牌研究有限公司 | Co-initiated polyether polyol and process for its preparation |
| CN1133682C (en) * | 1999-01-22 | 2004-01-07 | 山东建筑材料工业学院 | Fire resistant polymer polylol and its use |
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