CN101484548B - Flame retardant composition - Google Patents

Abstract

A liquid flame retardant composition which comprises one or more flame retarding agents, which are the epoxides obtainable by reacting tetrabromobisphenol A with epichlorohydrin and their end-capped derivatives represented by Formula (1) is provided. The liquid composition is especially useful in the preparation of rigid polyurethane foams.

Description

Fire-retardant combination

The process of blend solid or wax-like not diffluent fire retardant usually need to heat and carries out equably in the Liquid precursor of urethane foam.Advantageously, provide fire retardant with the form of prefabricated (preformed) liquid composition, thereby need not under heating, to carry out the Blending Processes of urethane foam precursor, and therefore simplified significantly the process of making foams.Because the preparation of urethane foam is through the fact of outdoor the carrying out of being everlasting (for example in the job site (working site)), this may be useful especially.

The trial that addresses the above problem is described among WO 03/060000 and the US 4,717,509, and it relates separately to tetrabromo-bisphenol and tribromoneoamyl alcohol as the purposes of the fire retardant that is used for hard polyurethane foam.

The present invention relates to can be by the fire retardant class that tetrabromo-bisphenol (chemical name 4,4 '-isopropylidene-two (2,6-dibromophenol)) and epoxy chloropropane (chemical name chloromethyloxirane) reaction are obtained.The reaction of known tetrabromo-bisphenol and epoxy chloropropane produces various reactive epoxide with high bromine content, but their former states or with their form of capped derivatives as the fire retardant in the polymer composition.Above-mentioned epoxide and capped derivatives thereof represent with formula (1):

Wherein polymerization degree n is 0 to 5 and more preferably 0 to 4 integer, and R ₁And R ₂Be independently selected from following monoradical:

JP 64-074262 and JP 64-074263 propose the compound of formula (1) is used together with thermoplastic polyurethane.

Have now found that the combustioncharacteristics of hard polyurethane foam can advantageously be improved by before foaming stages above-mentioned solid or high viscosity epoxide and capped derivatives thereof being introduced in the reaction mixture.It has also been found that in the mixture that one or more these solids of sizable amount or high viscosity fire retardant and its structural similitude thing can be dissolved in as the liquid of polyvalent alcohol or phosphoric acid ester or described two kinds of liquid, so that stable liquid composition to be provided, at room temperature during the standing storage, this stable liquid composition has stoped the precipitation of described fire retardant basically.The stable liquid composition of gained can be advantageously used in fire retardant is transported to foaming system, with permission they is incorporated in the hard polyurethane foam.

Therefore, the invention provides a kind of liquid flame-proof composition, it comprises:

A) one or more fire retardants that represent with following structural (1):

Wherein polymerization degree n is 0 to 5 and more preferably 0 to 4 integer, and R ₁And R ₂Be independently selected from following monoradical:

With

B) one or more are selected from the liquid of polyvalent alcohol and phosphoric acid ester.

Preferably, this liquid composition comprises the fire retardant with following formula (1 ') expression:

Wherein m is weight average degree of polymerization and in 0.05 to 1.0 scope, and more preferably in 0.05 to 0.7 scope, and R ₁And R ₂As mentioned above.The particularly preferred fire retardant that drops in following formula (1) scope is the mixture that comprises with the symmetrical ring epoxy resins of following formula (1a) expression:

Wherein weight average degree of polymerization m is in 0.05 to 0.5 scope.More particularly, have with the epoxy-capped fire retardant of formula (1a) expression and be not less than 350g/eq (wherein m equals 0.063), more preferably be not less than 370g/eq (wherein m equals 0.113) even more preferably at 380 average epoxy equivalent (weight)s (epoxy equivalent weight) in the scope of 420g/eq.Epoxy equivalent (weight) (EEW) is defined as the molecular weight of material divided by the epoxide group number that wherein contains, and can (for example measure by method well known in the prior art, " Encyclopedia of polymer science and engineering ", John Wiley﹠amp; Sons, the 6th volume (1986)).

Therefore provide with the form of the mixture that comprises following epoxide with the fire retardant of formula (1a) expression:

(1a-I) monomer of tetrabromo-bisphenol diglycidylether, wherein in formula (1), n equals 0 and R ₁And R ₂All be glycidyl, shown in (1a-I):

The epoxy equivalent (weight) of this monomer is 328g/eq.

(1a-II) dimer of tetrabromo-bisphenol diglycidylether, wherein in formula (1), n equals 1 and R ₁And R ₂All be glycidyl, shown in (1a-II):

This dimeric epoxy equivalent (weight) is 628g/eq.

(1a-III) tripolymer of tetrabromo-bisphenol diglycidylether, wherein in formula (1), n equals 2 and R ₁And R ₂It all is glycidyl.This trimerical epoxy equivalent (weight) is 928g/eq.

Most preferably, preferably the fire retardant by formula (1a) expression is the mixture with average epoxy equivalent (weight) of 385-415g/eq, this mixture mainly is comprised of the monomer of formula (1a-I) and the dimer of formula (1a-II), and wherein the higher oligomer of the diglycidylether of tripolymer (1a-III) and possible tetrabromo-bisphenol exists to be not more than 15% total amount.The preferred distribution (profile) of the molecular weight distribution of the various Resins, epoxy of the fire retardant of the constitutional formula (1a) that can measure by gel permeation chromatography (GPC) following (these scopes represent with the weight percent with respect to the gross weight of the fire retardant of formula (1a)):

(1a-I) monomer of expression: 55-70%

(1a-II) dimer of expression: 20-35%

(1a-III) tripolymer of expression: 5-10%

Higher oligomers: be less than 5%

The fire retardant of formula (1a) expression can by method preparation well known in the prior art, also be available commercially.For example, the fire retardant that has a formula (1a) of the average epoxy equivalent (weight) of about 400g/eq can be commercially available by trade(brand)name F-2001 (Dead Sea Bromine Group).Hereinafter, said mixture is called " F-2001 ".The fire retardant of formula (1a) normally by make tetrabromo-bisphenol and epoxy chloropropane under the existence of alkali (for example, aqueous sodium hydroxide solution), randomly at inert solvent for example in toluene or the methyl iso-butyl ketone (MIBK), reaction is made under heating.After being separated, washing the organic phase that contains product with water with from wherein removing residual salt, and finally reclaim product by the distillation organic solvent.The average epoxy equivalent (weight) of product, i.e. formula (1a-I), (1a-II) and the distribution of various Resins, epoxy in product mixtures (1a-III) can be controlled by the ratio of adjusting each reactant.The concentration of the epoxy chloropropane that uses is lower, and the epoxy equivalent (weight) of gained mixture is higher.

Another subclass that preferably drops on the fire retardant in formula (1) scope comprises the derivative of tribromophenol end-blocking, wherein terminal units R ₁And R ₂Represent by following formula:

Therefore, preferred fire retardant to be used according to the present invention comprises the tribromophenol end-caps that one or more represent with formula (1b):

Wherein n is 0 to 5 and more preferably 0 to 4 integer.More particularly, fire retardant to be used according to the present invention is the tetrabromo-bisphenol-epichlorohydrin resin of two (2,4,6-tribromo-benzene phenolic ether) end-blockings, and it provides with the form that comprises by the various mixtures of these independent derivatives of (1b) expression:

Wherein n equals 0,1 and 2.Hereinafter, these independent compounds are expressed as follows respectively: the monomer of formula (1b), be abbreviated as (1b-I); The dimer of formula (1b) is abbreviated as (1b-II); And the tripolymer of formula (1b), be abbreviated as (1b-III).

According to an embodiment of the invention, above-mentioned resin provides with the form of mixture basically composed as follows that (composition of mixture can be measured by GPC; Each scope represents with the weight percent for the gross weight of mixture of Compound Phase independently): monomer (1b-I): 55-70%, and preferred about 65-70%; Dimer (1b-II): 20-35%, and preferred about 25-30%; Tripolymer and more senior oligomer (1b-III): 5-15%, and preferred about 5-10%.

According to selectable embodiment, above-mentioned resin provides with the form of mixture, and this mixture comprises: monomer (1b-I): 30-50%, and preferred about 35-45%; Dimer (1b-II): 5-15%, and preferred about 7-13%; Tripolymer (1b-III): 5-20%, and preferred about 10-15%.More senior oligomer: 20-40%, and preferred about 25-35%; With the compound that is less than 10% formula (1), wherein terminal units R ₁And R ₂Different.

The above-mentioned subclass of fire retardant comprises the tribromophenol end-caps that one or more represent with formula (1b):

Wherein n is 0 to 5 and more preferably 0 to 4 integer, this subclass of fire retardant can be by method preparation well known in the prior art, (for example also be available commercially, by F-3014 and F-3020 that Dead Sea Bromine Group makes, it corresponds respectively to the first and the second mixture of above-mentioned composition).Tribromophenol end-blocking resin (1b) also can be by making formula (1a) expression mixture and the tribromophenol (may in solvent) of Resins, epoxy react and obtain.This reaction is being carried out under heating under the existence of catalyzer (for example, based on Li catalyzer) or mineral alkali (for example sodium hydroxide or potassium hydroxide) or organic bases (for example tertiary amine, quaternary ammonium salt Huo quaternary alkylphosphonium salt).Preparation process is as described below.

Should be noted that fire retardant to be used according to the present invention can comprise symmetrical and asymmetric derivative (wherein, the R in the formula (1) ₁And R ₂Identical or different respectively).

As explained above, the invention provides and contain with following formula (1) expression, more particularly, use the liquid composition of the fire retardant of formula (1a) and formula (1b) expression.This liquid composition is uniformly basically, contains fire retardant that useful described each structural formula represents from the formation of the separation phase of liquid medium so that basically stoped.Term herein " basically stop " is used for that the express liquid composition can be clarified, stable solution or the form that wherein forms the composition of second-phase (for example precipitation) exist, and the amount that wherein said second-phase contains fire retardant is no more than 5% of the total amount of fire retardant described in the said composition.

Preferably, the weight concentration of fire retardant in composition of the present invention of formula (1) is 10% to 60%, and more preferably 20% to 45%, so that the bromine content of composition provided by the invention is not less than 5%, and preferably be not less than 15% (w/w).More preferably, bromine content is not less than 25% (w/w).

That the fire retardant of permission formula (1) dissolves therein, be ester (phosphoric acid ester) or its mixture of polyvalent alcohol or phosphoric acid according to the liquid component of composition of the present invention.

Term " polyol " used herein refers to contain the compound of two or more hydroxyls, and preferably refers to be the polyethers that contains hydroxyl or the polymkeric substance that contains hydroxyl of polyester.As polyvalent alcohol, preferably use its hydroxyl value to be not less than 3 polyvalent alcohol or the mixture of this polyvalent alcohol.According to an embodiment, be polyether glycol with polyvalent alcohol used according to the invention.This class polyvalent alcohol obtains by the opening of one or more oxyalkylenes (for example, ethylene oxide and propylene oxide) with the suitable reactants that contains active hydrogen atom (for example alcohol, amine and acid); More particularly, described reactant can be selected from dibasic alcohol, trivalent alcohol, novolac resin (novolac resins), tetramethylolmethane, Sorbitol Powder, sucrose, quadrol, diethylenetriamine etc.According to the present invention, also can use polyester polyol; This class polyvalent alcohol obtains by the condensation reaction with dibasic alcohol and trivalent alcohol (for example, ethylene glycol, propylene glycol, glycol ether etc.) such as dicarboxylic acid (or polycarboxylic acid) such as hexanodioic acid, phthalic acid etc.Particularly preferred polyvalent alcohol used according to the invention is based on the polyether glycol of glycerine.The hydroxyl value of this polyvalent alcohol is preferably in the scope of 150-850mg KOH/g, and more preferably in the scope of 200-600mg KOH/g.Term " hydroxyl value " refers to the number of the reactive hydroxyl that can be used for reacting, and represents with the milligram number of the potassium hydroxide of the hydroxy radical content that is equivalent to a gram sample.

Polyvalent alcohol used according to the invention can be non-halogenated polyol or halogenated polyol or its mixture.For example, halogenated polyol is described in US 4,067, and in 911, it is incorporated herein by reference.Yet preferred is non-halogenated polyol.

Polyol phase is preferably 10% to 70% for the weight concentration of composition total weight, and more preferably 20% to 60%, and most preferably be 40% to 60%.

As the ester of the pentahydric acid of phosphorus, namely phosphoric acid ester is preferably used halogenated alkyl phosphate, and more specifically, chloroalkyl phosphate esters.Particularly preferably be three ester cpds-trialkyl phosphates, for example three (monochloro alkyl) phosphoric acid ester or three (dichloro alkyl) phosphoric acid ester, particularly preferably three (2-chloropropyl) phosphoric acid ester.Term " alkyl " preferably refers to C ₁-C ₅Alkyl.It should be noted that phosphoric acid ester can be symmetrical or asymmetric, contain identical or different alkyl respectively.

Phosphoric acid ester is preferably 10% to 70% with respect to the weight concentration of composition total weight, and more preferably 20% to 60%, and most preferably be 40% to 60%.

Composition according to the present invention is by being prepared as follows: the fire retardant of an amount of formula (1) is heated (preferably under agitation) with liquid ingredient until obtain settled solution, cool off subsequently this liquid composition and storage until use, wherein this liquid ingredient is ester or its mixture of the pentahydric acid of polyvalent alcohol or phosphorus.

More preferably, composition according to the present invention is by being prepared as follows: liquid ingredient is incorporated in the suitable container, be heated the first temperature in the 50-60 ℃ of scope, the fire retardant (preferably under agitation) of formula (1) is joined in the described container, and with second temperature of gained mixture heating up in 65-100 ℃ of scope.Usually obtain clear soln in heating under described the second temperature after about 60-120 minute.Then cool off this mixture so that the liquid flame-proof composition of the present invention of clarification, stable solution form to be provided.

Liquid composition can at room temperature keep the form at least 50 days of stabilizing solution, and more preferably at least 70 days, and even more preferably at least 90 days.Concerning this specification sheets, room temperature is 20-25 ℃.According to another embodiment, this liquid composition can be-18 ℃ of lower forms that keep stabilizing solutions at least 3 days.The aforementioned stable property testing can be undertaken by following: according to compositions related manufacturing liquid flame retardant, under corresponding conditions, store this liquid flame retardant, and after the storage time of above appointment (waiting period), observe said composition to determine wherein whether to exist throw out.

Also have been found that, at room temperature for solid, also can successfully be dissolved in the stability that does not change said composition in the liquid composition provided by the invention by the fire retardant tribromoneoamyl alcohol of the representation of formula 2 so that keep the solution form during the at room temperature standing storage of resulting composition:

(formula 2)

And, having been found that the fire retardant of formula (1) and the combination of tribromoneoamyl alcohol in liquid composition of the present invention are useful especially for the expection application that is used for urethane foam, it will discuss in more detail and the example explanation below.Preferably, the weight concentration of tribromoneoamyl alcohol is with respect to 10% to 50% of said composition gross weight, and more preferably 20% to 40%.When preparation comprises the composition of tribromoneoamyl alcohol, according to above-mentioned preparation process, wherein tribromoneoamyl alcohol was incorporated in the described liquid before or after the fire retardant of adding formula (1).Tribromoneoamyl alcohol can be commercially available from Dead Sea Bromine Group by trade(brand)name FR-513.The method for preparing tribromoneoamyl alcohol is described in US3, in 932,541.

Particularly preferred liquid flame-proof composition according to the present invention is the solution of the tribromoneoamyl alcohol of the fire retardant (more preferably above-mentioned formula (1a) or fire retardant (1b)) that comprises the formula (1) of the 20-40 % by weight that is dissolved in one or more solvents and 20-40 % by weight, described solvent is selected from non-halogenated polyether-polyvalent alcohol (more particularly, polyethers-polyvalent alcohol (for example Alcupol C-5710) based on glycerine) and contain the phosphoric acid ester (more particularly, three (2-chloropropyl) phosphoric acid ester) of halogen atom.The weight percent that more than provides is with respect to the gross weight of said composition.

Should be noted that this liquid composition can contain the expection that usually can be used for fire-retardant combination and use, namely be used for the extra composition of the preparation of hard polyurethane foam.For example, said composition can comprise for the antioxidant of stable existence in the polyol solvent of said composition, and preferably its concentration is up to 2000ppm.Phenol antioxidant most preferably, it can be selected from 2,6-di-t-butyl-p-cresol, 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene-bis (4,6-DI-tert-butylphenol compounds) and 3,5-di-t-butyl-4-hydroxyl phenylpropionic acid stearyl, and composition thereof.

Novel compositions of the present invention can be used as the fire retardant for urethane and polyisocyanurate foam especially.As explained above, liquid composition provided by the invention is the solution of the fire retardant (more preferably formula (1a) and fire retardant (1b)) that contains formula (1) and optional tribromoneoamyl alcohol as solute, therefore and can directly add in the liquid mixture for the preparation of the reactant of urethane and polyisocyanurate foam, significantly simplify thus the blend operation of described mixture and in described mixture, obtained easily the even distribution of component that will reaction.

Therefore, novel flame-retardant composition of the present invention can be joined and be suitable for obtaining in the standard recipe of hard polyurethane foam (by continuous, discontinuous or spray method) or polyisocyanurate foam.Therefore, on the other hand, the invention provides a kind of method, it comprises:

The prefabricated liquid composition of the fire retardant (the more preferably fire retardant of formula (1a) or formula (1b)) that contains formula (1) is provided, wherein described fire retardant is dissolved in the liquid that comprises one or more polyvalent alcohols and/or one or more phosphoric acid ester, wherein tribromoneoamyl alcohol preferably is present in the described liquid composition; With

Described liquid composition is mixed with one or more polyvalent alcohols of additional quantity, thereby the polyol component that is suitable for preparing urethane or polyisocyanurate foam is provided.

Term " polyol component " refers to react the total amount with the polyvalent alcohol that foams are provided.Usually, anti-flaming liquid composition of the present invention comprises the polyol component of about 10-40 % by weight.Make subsequently gained polyol component and isocyanate component in the presence of whipping agent and catalyzer, react to obtain urethane or polyisocyanurate foam.

Use the liquid composition of the fire retardant (preferably using with tribromoneoamyl alcohol) that contains formula (1) so that final foams can satisfy the requirement of DIN 4102 B2 test with the amount of abundance.The bromine content of final foams is no less than 1% usually.Preferably, regulate the amount of liquid composition of the present invention, so that the bromine content of final foams is with respect to 1% to 15%, more preferably 2% to 10%, most preferably 2% to 5% of foams gross weight.

If necessary, the method for the preparation of polyol component according to the present invention can be carried out easily on the spot.Prefabricated liquid composition and one or more polyvalent alcohols (for example polyethers-polyvalent alcohol listed above and polyester-polyvalent alcohol) that will contain the fire retardant (preferably with tribromoneoamyl alcohol) of formula (1) mix to provide the polyol component of foams on the spot, subsequently whipping agent and catalyzer and possible tensio-active agent are added in the described polyol component.This mixing step can at room temperature carry out on the spot in the job site providing and contains wherein that the fact of the polyol component of equally distributed fire retardant has consisted of the most important advantage of the present invention.

Suitable whipping agent used according to the invention is as known in the art and for example comprises, water (it produces carbonic acid gas with isocyanate reaction the time) and low boiling organic liquids, for example pentane or halohydrocarbon (for example, methylene dichloride).The amount of this whipping agent can change in wide scope.

As the catalysts that is intended to accelerate the reaction between polyvalent alcohol and the vulcabond component, usually use aromatics and/or aliphatic amine or organic metal salt or its mixture.Amine catalyst can be selected from triethylenediamine, dimethylethanolamine (DMEA), tetramethyl butane diamine (TMBDA), dimethylcyclohexylamine (DMCHA) and triethylamine (TEA).Organic metal salt is preferably based on following metal: tin, zinc, manganese, magnesium, bismuth, antimony, lead and calcium.Particularly preferably be the Bivalent Tin compound, for example stannous octoate and stannous dibutyl tin laurate.Preferably, this catalyzer with respect to the weight concentration of polyol component in 1 % by weight in the scope of 5 % by weight.

In the preparation of urethane foam, also usually use 2% a small amount of, as to be up to polyol component weight tensio-active agent.For this reason, can use silicone resin.

Formed contain above-mentioned catalyzer, whipping agent and be dissolved in the polyol component of tensio-active agent wherein after, make described polyol component and isocyanate component react to provide required foam.Suitable isocyanic ester used according to the invention can be selected from aliphatic polyisocyante, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanate or heterocycle polyisocyanates, for example 4,4 '-diphenylmethanediisocyanate, toluylene group diisocyanate, sec.-propyl vulcabond and hexamethylene diisocyanate.The amount of the vulcabond that the manufacturing foams are required is calculated according to any hydroxyl value that other contains the compound of reactive hydrogen of polyol component and existence.Also can a little excessively use vulcabond.

Hard polyurethane foam can be by continuous, discontinuous or spray method preparation well known in the art.

In discontinuous method, all components mixed and pour into usually by in wooden or the metal mould to form foams.The one suitable period (depending on system and die size) afterwards, foams are taken out from this mould as piece material (block).This piece material is solidified, then be cut to plate, half shell (half shells) or other shape.

In continuation method, reaction mixture is distributed on the transfer roller from transverse shifting head (traversing head), this transfer roller is coated with paper to promote the disengaging of foams.Between the phase of expansion of foams, the side is supported with vertical conveyor.At the end of foaming production line, foams are cut into bun (buns) and store specific time.Subsequently, these foams can be cut into the shape of expectation.

Spray technique is used for filling mould and plate and is used for foams are applied to the plate surface.Be sprayed at wherein relate in the large-area application (for example tank or building wall) particularly useful.Spraying hard foam coating both provided physical strength that improved insulativity also is provided.

As already pointed out, the compound of formula 1 also is not proposed for the combustibility that reduces hard polyurethane foam up to now.Therefore, the invention still further relates to the method for preparing the flame retarded rigid polyurethane foams body, it comprises makes polyol component and vulcabond component react to form hard polyurethane foam in the presence of following material: above-mentioned one or more are with above-mentioned formula (1), and fire retardant, at least a whipping agent, at least a catalyzer, at least a tensio-active agent and at least a phosphoric acid ester more preferably using formula (1a) or (1b) represent.The gained hard polyurethane foam is characterised in that concentration is preferably the structural unit corresponding to formula (1a) or fire retardant (1b) with respect to the 1%-5% of foams gross weight; This hard polyurethane foam forms another aspect of the present invention.

Following Preparation Example illustrates preferred implementation of the present invention.

Embodiment

Preparation 1

The fire retardant of preparation formula 1 (b)

Add the brominated epoxy resin (can be used as F-2001 is purchased) that 100 grams have following properties in the 1L glass kettle that agitator, electric mantle, thermometer and reflux exchanger are housed: 398 g/mols EEW and 49% bromine content (w/w), 300 gram methyl iso-butyl ketone (MIBK) and 155 restrain tribromophenols.Stir this mixture until then all solids dissolving adds 0.75 gram Tributylamine.Slowly the reacting by heating mixture to be refluxing, and should reaction continue 6 hours.

After being cooled to room temperature, with this reaction mixture of distilled water wash 3 times, contain subsequently being separated of water.Finally under 160 ° of vacuum, distill methyl iso-butyl ketone (MIBK).Obtain the resin according to formula (1b) that 250 grams have following character:

Softening temperature: 101 ℃

Molecular-weight average (measuring by GPC): 1460

Bromine content: 59 % by weight.

(for example can pass through the weight ratio of change reactant, make 574 gram YDB 400 or F-2001,294.6 gram tribromophenols and 127 gram tetrabromo-bisphenols reactions) revise above-mentioned steps with the different resins of acquisition formula (1b), namely comprise the tripolymer of dimer, formula (1b-III) of monomer (1b-I), the formula (1b-II) of different ratios and the mixture of more senior oligopolymer.

Embodiment 1-6

The liquid flame-proof composition that contains the Resins, epoxy of formula (1a)

The composition of several liquid flame-proof prescription of the present invention summed up by table 1 and about its stability test, described composition is based on fire retardant or the fire retardant of formula (1a) and the combination of tribromoneoamyl alcohol of formula (1a).Preparation process is as follows substantially:

In the 0.5L reactor of mechanical stirrer, thermometer and reflux exchanger is housed, pack into liquid ingredient (non-halogenated polyether polyvalent alcohol, it is Alcupol C-5710; Or the organophosphate of halogen replacement, it is three (2-chloropropyl) phosphoric acid ester (TCPP); Or their mixture) and be heated to 60 ℃.Then fire retardant (F-2001 or F-2001 and follow-up FR-513 (perhaps vice versa)) is joined in the reactor, afterwards, temperature is elevated to 70-100 ℃.The gained mixture was heated about 2 hours under 70-100 ℃, until obtain clear soln.After being cooled to room temperature, obtain stable solution.

Table 1. is based on the composition of F-2001

Embodiment	F-2001, % by weight	FR-513, % by weight	TCPP, % by weight	C5710 (polyvalent alcohol), % by weight	Hydroxyl value	Br, % by weight	Stability, fate
								1	60	-	40	-	～0	～30	～180
2	20	30	50	-	52	～32	～180
								3	30	30	40	-	52	～36	～180
4	20	30	-	50	337	～32	～180
								5	60	-	20	20	114	～30	～180
6	20	30	30	20	166	～32	～180

The stability number value representation that provides stores at ambient temperature in said composition and does not form the length of sedimentary time.Test is still being proceeded, and therefore given numerical value is not the ultimate value of stability.

The fire retardant of liquid composition of the present invention in the standard recipe that acts on hard polyurethane foam.These foams prepare (being respectively the following example 7-11 and embodiment 12-16) by continuous or discontinuous method.

Except anti-flaming liquid composition of the present invention, in the preparation of urethane foam, also use following raw materials according:

Be used for the quantity-produced polyvalent alcohol:

1. the Terol 516-polyester polyol that has the hydroxyl value of 305mg KOH/g.

2. the Fox-O-Pol M530-polyvalent alcohol that has the hydroxyl value of 530mg KOH/g.

3. glycerine.

The polyvalent alcohol that is used for Discontinuous manufacture:

1.Alcupol R-2510-has (glycerol initiated) polyether glycol that begins with glycerine of the hydroxyl value of 250mg KOH/g.

2.Alcupol C-5710-has the polyether glycol that begins with glycerine of the hydroxyl value of 570mg KOH/g.

3.Alcupol R-4720-has the polyether glycol that begins with Sorbitol Powder of the hydroxyl value of 475mg KOH/g.

Auxiliary chemicals

The DMCHA dimethylcyclohexylamine

AM 58 catalyst for trimerization

DC 193 organic silicon surfactants

TCPP three (chloropropyl) phosphoric acid ester

TEP triethylene phosphoric acid ester

Pentane foaming agent

Isocyanic ester

MDI: poly-diphenylmethanediisocyanate

Embodiment 7-11

Be used for using the continuous system for preparing hard polyurethane foam based on the liquid flame-proof composition of F-2001

The foams preparation process is as follows:

The fire-retardant combination based on F-2001 (being abbreviated as " FR of embodiment x " in the following table 2), phosphoric acid ester and the catalyzer of polyvalent alcohol, water, tensio-active agent, embodiment 2-6 are weighed, placed the mixing beaker, also mix to form homogeneous solution.Pentane is added in this solution, and after extra mixing, add polymeric isocyanate (polymeric isocyanate).Stirred this mixture 6 seconds and pour in another beaker with 3000rpm.The foams that form are remained under the room temperature at least 24 hours, then from beaker, take out and cut into sample with saw.Then according to the combustibility (15.0cm or less flame height show that these foams have passed through test) of DIN 4102 B2 test procedure specimen.Table 2 has been summed up the composition of the preparation that is used for foams and the test result of parameter and foams.

Table 2. uses based on pentane-blown (pentane-blown) the B2 continuous system of the composition of F-2001 (20 ℃ of lower mixing)

Composition (gram)	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11
						M530	30	30	30	30	30
Terol 516	30	30	30	30	30
						Glycerine	7	7	5	5	5
The FR F-2001/FR-513/TCPP of embodiment 2 20: 30: 50	37.2
						The FR F-2001/FR-513/TCPP of embodiment 3 30: 30: 40		37.2
The FR F-2001/FR-513/C5710 of embodiment 4 20: 30: 50			37.2
						The FR F-2001/TCPP/C5710 of embodiment 5 60: 20: 20				37.2
The FR F-2001/FR-513/TCPP/C5710 of embodiment 6 20: 30: 30: 20					37.2

TCPP	20	20	20	20	20
						TEP	2.8	2.8	2.8	2.8	2.8
DMCHA	2	2	2	2	2
						AM58	1	1	1	1	1
DC193	1.5	1.5	1.5	1.5	1.5
						Water	2.49	2.49	2.49	2.49	2.49
Pentane	13.2	13.2	13.2	13.2	13.2
						Add up to	147.19	147.19	145.19	145.19	145.19
Isocyanic ester, gram (Urestyl-10)	154.57	154.57	173.72	150.84	156.17
						Mixing time, second	6	6	6	6	6
Cream time, second	12	12	13	12	12
						Gel time, second	33	32	39	32	34
Tack-free time, second	38	39	45	36	40
						Set time, second	118	125	115	94	121
Br content in the polyol blends, % by weight	8.9	10.2	9.0	8.5	9.0
						Br content in the foams, % by weight	4.2	4.8	3.9	4.0	4.2
Flame height, cm (DIN 4102)	8.9	7.6	9.1	8.8	8.5

In table 2 (and in following table 3 and 5), the parameter-definition that relates to the foams preparation is as follows:

Cream time: the foams composition is from mixing beaker and discharge and beginning to produce time between the foams.

Gel time: the foams composition from mix beaker discharge adhere on the probe of introducing with foams and when probe is therefrom taken out foams extend time between moment of (string out).

Tack-free time: the foams composition loses its viscosity or the time between the adhering moment from the exterior skin that mixes beaker discharge and foams piece.

Set time: fully react completely to form required polymer property (such as intensity, dimensional stability, unit elongation etc.) the required time.

Embodiment 12-16

Be used for using the discontinuous system for preparing hard polyurethane foam based on the liquid flame-proof composition of F-2001

The step of foams preparation is as follows:

The fire-retardant combination based on F-2001 (being abbreviated as " FR of embodiment x " in the following table 3), phosphoric acid ester and the catalyzer of polyvalent alcohol, water, tensio-active agent, embodiment 2-6 weighed and place and mix beaker and mix to form homogeneous solution.In this solution, add polymeric isocyanate, then this mixture was stirred 15 seconds and poured in another beaker with 3000rpm.The foams that form are remained under the room temperature at least 24 hours, then from beaker, take out and cut into sample with saw.Then according to the combustibility (15.0cm or less flame height show that these foams have passed through test) of DIN 4102 B2 test procedure specimen.Table 3 has been summed up the composition of the preparation that is used for foams and the test result of parameter and foams.

Table 3. uses the discontinuous system of steeping in water for reconstitution bubble (water-blown) B2 (20 ℃ of lower mixing) based on the composition of F-2001

Composition (g)	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16
						R4720	35	35	35	35	35
R2510	20	20	23	23	23
						C5710	21	21	18	18	18
The FR F-2001/FR-513/TCPP of embodiment 2 20: 30: 50	20
						The FR F-2001/FR-513/TCPP of embodiment 3 30: 30: 40		20
The FR F-2001/FR-513/C5710 of embodiment 4 20: 30: 50			20
						The FR F-2001/TCPP/C5710 of embodiment 5 60: 20: 20				20
The FR of embodiment 6					20

F-2001/FR-513/TCPP/C5710 20∶30∶30∶20
						TCPP	25	25	25	25	25
DMCHA	0.9	0.9	0.9	0.9	0.9
						DC 193	1.5	1.5	1.5	1.5	1.5
Water	4.6	4.6	4.6	4.6	4.6
						Add up to	128	128	128	128	128
Isocyanic ester, gram	167.00	167.00	179.50	167.73	170.48
						Mixing time, second	15	15	15	15	15
Cream time, second	25	25	25	25	25
						Gel time, second	102	107	121	120	107
It is glutinous to disappear, the time	231	209	220	239	216
						Br content in the polyol blends, % by weight	5.0	5.8	5.0	4.7	5.0
Br content in the foams, % by weight	2.2	2.5	2.1	2.0	2.1
						Flame height, cm (DIN 4102)	9.4	11.8	11.4	13.0	11.6

Embodiment 17-27

The liquid flame-proof composition that contains the tribromophenol end-blocking resin of formula (1b)

The composition of several liquid flame-proof compositions of the present invention summed up by table 4 and to its stability test that carries out, said composition is based on fire retardant or the fire retardant of formula (1b) and the combination of tribromoneoamyl alcohol of formula (1b).Preparation process is as follows substantially:

In 0.5 liter of reactor of mechanical stirrer, thermometer and reflux exchanger is housed, pack into liquid ingredient (non-halogenated polyether polyvalent alcohol, it is Alcupol C-5710; Or the organophosphate of halogen replacement, it is three (2-chloropropyl) phosphoric acid ester (TCPP); Or their mixture) and be heated to 50-60 ℃.Then fire retardant (F-3014 or F-3014 and follow-up FR-513 (perhaps vice versa)) is joined in the reactor, afterwards, temperature is elevated to 65-100 ℃.The gained mixture was heated about 2 hours under 65-100 ℃, until obtain clear soln.After being cooled to room temperature, obtain stable solution.

Table 4. is based on the composition of F-3014

Embodiment	F-3014, % by weight	FR-513, % by weight	TCPP, % by weight	C5710 (polyvalent alcohol) % by weight	Hydroxyl value	Br, % by weight	Stability, fate
								17	60	-	40	-	48	36	～180
18	20	30	50	-	68	34	～180
								19	30	30	40		76	37	～180
20	20	30	-	50	353	34	～180
								21	20	25		55	373	30	～180
22	20	20		60	393	27	～180
								23	20	30	10	40	296	34	～180
24	20	30	20	30	239	34	～180
								25	20	40	-	40	313	41	～180
26	20	40	25	15	173	41	～180
								27	15	30	-	55	379	31	～180

The stability number value representation said composition that provides has stored at ambient temperature and has not formed the length of sedimentary time.Test is still being proceeded, and these numerical value that therefore provide are not the ultimate values of stability.

Embodiment 28-38

Be used for using the continuous system for preparing hard polyurethane foam based on the liquid flame-proof composition of F-3014

The composition of embodiment 17-27 is used for preparing hard polyurethane foam according to the following step:

The fire-retardant combination based on F-3014 (being abbreviated as " FR of embodiment x " in the following table 5), phosphoric acid ester and the catalyzer of polyvalent alcohol, water, tensio-active agent, embodiment 17-27 weighed and place and mix beaker and mix to form homogeneous solution.Pentane is added in this solution, and after extra mixing, add polymeric isocyanate.This mixture was stirred 6 seconds and poured in another beaker with 3000rpm.The foams that form are remained under the room temperature at least 24 hours, then from beaker, take out and cut into sample with saw.Then according to the combustibility (15.0cm or less flame height show that these foams have passed through test) of DIN 4102B2 test procedure specimen.Table 5 has been summed up the composition of the preparation that is used for foams and the result of parameter and foams test.

Table 5. uses based on the pentane-blown B2 continuous system of the composition of F-3014 (20 ℃ of lower mixing)

Composition, gram	Embodiment 28	Embodiment 29	Embodiment 30	Embodiment 31	Embodiment 32
						M530	30	30	30	30	30
Terol 516	30	30	30	30	30
						Glycerine	7	7	7	5	5
The FR F-3014/TCPP of embodiment 17 60: 40	37.2
						The FR F-3014/FR-513/TCPP of embodiment 18 20: 30: 50		37.2
The FR F-3014/FR-513/TCPP of embodiment 19 30: 30: 40			37.2
						The FR F-3014/FR-513/C5710 of embodiment 20 20: 30: 50				37.2
The FR F-3014/FR-513/C5710 of embodiment 20 20: 25: 55					37.2
						TCPP	20	20	20	20	20
TEP	2.8	2.8	2.8	2.8	2.8
						DMCHA	2	2	2	2	2
AM58	1	1	1	1	1
						DC193	1.5	1.5	1.5	1.5	1.5
Water	2.49	2.49	2.49	2.49	2.49
						Pentane	13.2	13.2	13.2	13.2	13.2
Add up to	147.19	147.19	147.19	145.19	145.19
						Isocyanic ester, gram (Urestyl-10)	154.36	156.21	157.03	174.54	176.59
Mixing time, second	6	6	6	6	6
						Cream time, second	11.5	11.5	11.5	12.5	12

Gel time, second	32	32	32	37	38
						Tack-free time, second	36	35	37	43	42
Set time, second	93	99	108	112	106
						Br content in the polyol blends, % by weight	10.0	9.5	11.2	9.6	8.6
Br content in the foams, % by weight	4.7	4.4	5.2	4.2	3.7
						Flame height, cm (DIN 4102)	9.3	11.3	9.3	11.4	11.8

Table 5. (continuing)

Composition, gram	Embodiment 33	Embodiment 34	Embodiment 35	Embodiment 36	Embodiment 37	Embodiment 38
							M530	30	30	30	30	30	30
Terol 516	30	30	30	30	30	30
							Glycerine	5	5	5	5	7	5
The FR F-3014/FR-513/C5710 of embodiment 22 20: 20: 60	37.2
							The FR F-3014/FR-513/TCPP/ C5710 of embodiment 23 20: 30: 10: 40		37.2
The FR F-3014/FR-513/TCPP/ C5710 of embodiment 24 20: 30: 20: 30			37.2
							The FR F-3014/FR-513/C5710 of embodiment 25 20: 40: 40				37.2
The FR F-3014/FR-513/TCPP/ of embodiment 26					37.2

C5710 20∶40∶25∶15
							The FR F-3014/FR-513/C5710 of embodiment 27 15: 30: 55						37.2
TCPP	20	20	20	20	20	20
							TEP	2.8	2.8	2.8	2.8	2.8	2.8
DMCHA	2	2	2	2	2	2
							AM58	1	1	1	1	1	1
DC193	1.5	1.5	1.5	1.5	1.5	1.5
							Water	2.49	2.49	2.49	2.49	2.49	2.49
Pentane	13.2	13.2	13.2	13.2	13.2	13.2
							Add up to	145.19	145.19	145.19	145.19	147.19	145.19
Isocyanic ester, gram (Urestyl-10)	178.64	169.51	163.66	171.26	166.98	178.03
							Mixing time, second	6	6	6	6	6	6
Cream time, second	12	12	12	12	12	12
							Gel time, second	38	35	34	34	34	37
Tack-free time, second	44	42	37	40	36	43
							Set time, second	100	95	94	106	109	99
Br content in the polyol blends, % by weight	7.5	9.6	9.6	11.7	11.5	8.8
							Br content in the foams, % by weight	3.2	4.2	4.3	5.1	5.2	3.8
Flame height, cm (DIN 4102)	12.4	9.9	10.1	10.3	9.1	11.5

Embodiment 39-42

The liquid flame-proof composition that contains the tribromophenol end-blocking resin of formula (1b)

Table 6 shows the composition of several liquid flame-proof compositions of the present invention and to its stability test that carries out, described composition is based on fire retardant or the fire retardant of formula (1b) and the combination of tribromoneoamyl alcohol of formula (1b).Described composition is by obtaining described composition in 70-90 ℃ of lower mixing and subsequently cooling.

Table 6. is based on the composition of F-3014 and/or F-3020

Embodiment	F-3014, % by weight	F-3020, % by weight	FR-513, % by weight	C5710, % by weight	Terol 516, % by weight	R-4720, % by weight	Hydroxyl value	Br, % by weight	Stability, month number
										39	20	-	30	-	50	-	222	34	6
40	20	-	30	-	-	50	307	34	6
										41	-	20	30	50	-	-	345	33	2
42	10	10	30	50			345	34	2

^*Provide that stability number value representation composition has stored at ambient temperature and the length that do not form the sedimentary time.Test is still being proceeded, and the numerical value that therefore provides is not the ultimate value of stability.

Embodiment 43-46

Be used for using the continuous system for preparing hard polyurethane foam based on the liquid flame-proof composition of F-3014 and/or F-3020

The composition of embodiment 39-42 is used for preparing hard polyurethane foam according to previously described step.Table 7 has been summed up the composition of the preparation that is used for foams and the result of parameter and foams test.

Table 7. uses based on the pentane-blown B2 continuous system of the composition of F-3014 and/or F-3020 (20 ℃ of lower mixing)

Composition, gram	Embodiment 43	Embodiment 44	Embodiment 45	Embodiment 46
					M530	30	30	30	30
Terol 516	30	30	30	30
					Glycerine	5	5	5	5
The FR F-3014/FR-513/Terol 516 20 of embodiment 39: 30: 50	37.2
					The FR F-3014/FR-513/R-4720 of embodiment 40		37.5

20∶30∶50
					The FR F-3020/FR-513/C5710 of embodiment 41 20: 30: 50			37.2
The FR F-3014/F-3020/FR-513/C5710 of embodiment 42 10: 10: 30: 50				37.2
					TCPP	20	20	20	20
TEP	2.8	2.8	2.8	2.8
					DMCHA	2	2	2	2
AM58	1	1	1	1
					DC193	1.5	1.5	1.5	1.5
Water	2.49	2.49	2.49	2.49
					Pentane	13.2	13.2	13.2	13.2
Add up to	145.19	145.19	145.19	145.19
					Isocyanic ester, gram (Urestyl-10)	161.92	170.64	174.54	174.54
Mixing time, second	6	6	6	6
					Cream time, second	12	14	14	13
Gel time, second	31	36	36	37
					Tack-free time, second	41	49	49	52
Set time, second	136	102	98	97
					Br content in the polyol blends	9.6	9.6	9.3	9.6
Br content in the foams	4.3	4.2	4.0	4.2
					Flame height, cm, DIN 4102	11.6	11.7	11.7	11.9

Embodiment 47 (contrast)

The deliquescent comparison of various fire retardants

Make the structural similitude thing of tetrabromo-bisphenol, namely tetrabromo-bisphenol s (wherein sulphur bridge connects two aromatic rings) and epoxy chloropropane react the resemblance with the fire retardant that obtains formula 1a in Virahol.The gained reaction product (pass through by its structure ¹H NMR confirms) in methyl iso-butyl ketone (MIBK) and in the mixture of polyvalent alcohol and phosphoric acid ester, all have a solvability of non-constant, and therefore it can not be converted into its capped derivatives (resemblance of formula 1b), can not easily be transported in the polyurethane foam system.

Embodiment 48-49 (contrast)

To compare aspect their flame retarding efficiencies in hard polyurethane foam according to the composition of embodiment 20 (it is solution in polyvalent alcohol C5710 of the FR-513 of 20% F-3014 and 30% (has 34% bromine content)) and FR-513 50% solution (about 37% bromine) in polyvalent alcohol C5710., these two kinds of compositions are introduced in the continuous foamed system of pentane-blown for this reason, provided the foams described in following table 8.

Table 8. uses based on the pentane-blown B2 continuous system of the composition of F-3014 (20 ℃ of lower mixing)

Composition, gram	Embodiment 48	Embodiment 49
			M530	30	30
Terol 516	30	30
			Glycerine	5	5
The FR F-3014/FR-513/C5710 of embodiment 20 20: 30: 50	37.2
			FR-513/C5710 50∶50		37.2
TCPP	20	20
			TEP	2.8	2.8
DMCHA	2	2
			AM58	1	1
DC193	1.5	1.5
			Water	2.49	2.49
Pentane	13.2	13.2
			Add up to	145.19	145.19
Isocyanic ester, gram (Urestyl-10)	174.54	177.26
			Mixing time, second	6	6
Cream time, second	14	15

Gel time, second	37	36
			Tack-free time, second	51	51
Set time, second	88	90
			Br content in the polyol blends	9.6	10.4
Br content in the foams	4.2	4.5
			Flame height, cm (DIN 4102)	11.4	11.8

Data from table 8 can find out, composition of the present invention (flame height 11.4cm) demonstrates than only based on the good flame retardant resistance of FR composition (flame height 11.8cm) of FR-513, although bromine content is higher in the second composition.

Claims (25)

1. liquid flame-proof composition, it comprises:

A) one or more fire retardants that represent with formula (1):

Wherein polymerization degree n is 0 to 5 integer, and R ₁And R ₂Be independently selected from following monoradical:

With

B) one or more are selected from the liquid of polyvalent alcohol and phosphoric acid ester, and wherein said polyvalent alcohol comprises that having the polyvalent alcohol and the described phosphoric acid ester that are no less than 3 hydroxyls is replaced by halogen atom.

2. the liquid flame-proof composition of claim 1, wherein said fire retardant are with formula (1 ') expression:

Wherein m is weight average degree of polymerization and in 0.05 to 1.0 scope, and R ₁And R ₂With the definition in the claim 1.

3. the liquid flame-proof composition of claim 2, wherein said fire retardant are the Resins, epoxy with formula (1a) expression:

Wherein m is in 0.05 to 0.5 scope.

4. the liquid flame-proof composition of claim 3, the average epoxy equivalent (weight) of wherein said fire retardant is not less than 370g/eq.

5. the liquid flame-proof composition of claim 4, wherein said average epoxy equivalent (weight) at 380g/eq in the scope of 420g/eq.

6. the liquid flame-proof composition of claim 5, wherein said fire retardant is the mixture that comprises following Resins, epoxy:

(1a-I) monomer of tetrabromo-bisphenol diglycidylether:

(1a-II) dimer of tetrabromo-bisphenol diglycidylether:

(1a-III) tripolymer of tetrabromo-bisphenol diglycidylether, wherein n equals 2 in formula (1).

7. the liquid flame-proof composition of claim 1, wherein said fire retardant comprise that one or more are with the tribromophenol end-caps of formulas (1b) expression:

Wherein n is with the definition in the claim 1.

8. the liquid flame-proof composition of claim 7, wherein said fire retardant are that to comprise with n wherein be the mixture of the tribromophenol end-caps of 0,1 and 2 formula (1b) expression.

9. the liquid flame-proof composition of claim 8 is that the weight concentration of the tribromophenol end-caps of 0 and 1 formula (1b) expression is respectively 55-70% and 20-35% with n wherein wherein, with respect to the gross weight of the fire retardant of formula (1b).

10. the liquid flame-proof composition of claim 1, it at room temperature is the solution form.

11. the liquid flame-proof composition of claim 1, the weight concentration of the fire retardant of its Chinese style (1) is in the scope of 10% to 60% (w/w).

12. each liquid flame-proof composition among the claim 1-11, wherein said polyvalent alcohol is polyethers-polyvalent alcohol.

13. the liquid flame-proof composition of claim 12, wherein said polyethers-polyvalent alcohol is non-halo, and has and be no less than 3 hydroxyls.

14. the liquid flame-proof composition of claim 1, wherein said phosphoric acid ester are three (2-chloropropyl) phosphoric acid ester.

15. the liquid flame-proof composition of claim 1, it further comprises tribromoneoamyl alcohol.

16. the liquid flame-proof composition of claim 15, it is the solution that comprises the tribromoneoamyl alcohol of the fire retardant of formula (1) of the 20-40 % by weight that is dissolved in one or more solvents and 20-40 % by weight, and wherein said solvent is selected from polyethers-polyvalent alcohol and contains the phosphoric acid ester of halogen.

17. method for preparing the liquid flame-proof composition of claim 1, it comprises: with the fire retardant of formula claimed in claim 1 (1) with at least a be selected from as defined in claim 1 polyvalent alcohol and the liquid ingredient of phosphoric acid ester heat, until the acquisition clear soln is cooled off described liquid flame-proof composition and storage subsequently until use.

18. method for preparing the flame retarded rigid polyurethane foams body, it comprises makes polyol component with the hydroxyl value that is no less than 3 hydroxyls and has 150-850mg KOH/g and vulcabond component react in the presence of with the fire retardants of formula (1) expression and at least a whipping agent, at least a catalyzer and optional at least a tensio-active agent at one or more, wherein uses the fire retardant of formula (1) expression as follows:

Wherein polymerization degree n is 0 to 5 integer, and R ₁And R ₂Be independently selected from following monoradical:

19. the method for claim 18, wherein said fire retardant are the mixtures that comprises with the individually oriented compound of formula (1b) expression:

Wherein n equals 0,1 and 2.

20. the method that the polyol component that is suitable for preparing urethane or polyisocyanurate foam is provided, it comprises:

According to claim 1, liquid flame-proof composition be provided; With

Described liquid flame-proof composition is mixed with one or more polyvalent alcohols of additional quantity and optional at least a whipping agent, at least a catalyzer and at least a tensio-active agent.

21. the method for claim 20, wherein said liquid flame-proof composition further comprises tribromoneoamyl alcohol.

22. the method for claim 20, it at room temperature carries out on the spot in the job site.

23. the method for claim 20, wherein said liquid flame-proof composition are claim 7,8 or 9 described liquid flame-proof compositions, and are the solution form.

24. be used for to obtain the method for urethane or polyisocyanurate foam, it comprises makes according to claim 20 or polyol component and vulcabond component that 21 method obtains are reacted in the presence of at least a whipping agent, at least a catalyzer, at least a tensio-active agent and at least a phosphoric acid ester.

25. the hard polyurethane foam that can obtain by the method for claim 19 or 24, these foams comprise corresponding to one or more structural units with the compound of formula (1b) expression:

Wherein n equals 0,1 and 2.