BE598678A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



  Polymers.



   The present invention relates to uretane polymers having better flame-retardant and self-extinguishing properties; It relates more particularly to cellular polyurethanes, having much better flame-retardant and self-extinguishing properties. Its subject more especially is solid cellular polyurethane having these properties.



   Urethane polymers are well known, as are their manufacturing and processing processes into solid, semi-solid and flexible foam products. These polymers are formed by reacting a compound, the molecule of which contains at least 2 active hydrogen atoms and comprising a polyisocyanate,

 <Desc / Clms Page number 2>

 
 EMI2.1
 usually an aromatic type diisooyanate. These compounds include polyols, such as for example polyesters and polyitherns,
 EMI2.2
 To prepare a cellular foam product, we usually do
 EMI2.3
 reacting the polyol with an excess of polyisocyanate, to obtain a prepolymer, containing residual NCO groups.

   Normally 5-40% excess is used, the
 EMI2.4
 amount depending on the desired viscosity and the foam production process.
 EMI2.5
 A method of transforming the poly # 6thsne into foam is to add
 EMI2.6
 water, a catalyst and additional compounds of active hydrogen, as per
 EMI2.7
 .. ¯, 7, "'/' example of additional polyols. Water reacts with isooyanates, giving ...: 1 .. ¯,,,. G"., Q 1 carbon dioxide, which is locked in the Tisqusnse masss during the reaction. The catalyst promotes the crosslinking of the polymer chains and when the foam mass does not expand and reaches the hardening or baking point it contains several microscopic cells.

     '¯
 EMI2.8
 Another foam production process generally requires a
 EMI2.9
 less excess of polyisooyanate and the cell structure is obtained by using an inert liquid with a low ebnllitioa point, which is added at the same time
 EMI2.10
 that the catalyst and that the additional compound of active hydrogen ,. When the
 EMI2.11
 The reaction proceeds, no heat is formed and the "low boiling point liquid" does not evaporate. This Tapeur is enclosed in the cassa Tisqaause and hardening occurs as described above.

   Other methods are also known for the preparation of foamed urétha o polymers.
 EMI2.12
 Among the usual polyols, which are used in the foundation of
 EMI2.13
 pohnrethanea, there are the reaction products of polybasic acids, such as, for example, adipic, phthalic, sebacic, sucoinic, oxalic, ricinoleiquop etc. acids, with a polyalcohol, quej, such as for example ltetbylene glycol, diethylene glycol, propylene-glyool and butylene glycol, 1,4-butanediol glycerol, trimethylol-propane, trimethanol-ethane, 19296-hezanetriol, 1,2,4-butanetrioi, etc. Poly- ethera glycols have also been used.
 EMI2.14
 alkylene. The book entitled "Polyurethanes", by Bernard A.

   Dombrov, Reinhold
 EMI2.15
 hubliahin6 Corporation, New York, 1957, gives a good description of the poly-
 EMI2.16
 urethanes.
 EMI2.17
 Outra laur u% 31iaa% on in the manufacture of cellular products,

 <Desc / Clms Page number 3>

 urethane polymers are also used in other applications.



  For example, they can be cast in the form of films and used as a packaging material. They can be cast into molds, to form various articles, used in different applications. Urethane polymers have been used in the manufacture of rubbery articles and some have been used as adhesives. In general, these polymers are adaptable to uses which many polymers currently known to fulfill.



   A major drawback and therefore a factor limiting the possible uses of products made from polyurethanes is that they can easily ignite and burn. This remark is particularly true for foams. Although flame retardant compounds are known as well as methods of making them, particularly in textiles, the application of these compounds, added or mixed with cellular polyurethane, is not feasible.

   The deposition of a coating or the physical incorporation of these compounds into a foamed product is strictly limited, since the materials thus used are sensitive to migration, to solvents, to bad weather, to washing, etc. Consequently, the price of the initial treated product is increased, without achieving a strong permanent improvement in its flame retardant properties.



   Accordingly, a feature of the present invention resides in a method of forming a polyurethane having flame retardant properties,
 EMI3.1
 this process being characterized in that a polylsocyanate is reacted with a mixture of a polyol and of an organic phosphorus compound, the molecule of which contains at least 2 active hydrogen atoms; then the reaction product formed is cooked.



   Another characteristic of the present invention consists in converting, into foam ,, the reaction product of the polyisocyanate and the mixture of the polyol and the organic phosphorus compound, the molecule of which contains at least 2 active hydrogen atoms, then the mixture is cooked. foam product to form cellular polyurethane.



   Another feature of the present invention is to put
 EMI3.2
 nu nnint a KI1Y, 1st flame retardant of u.réth: m. in Isqusl l'ngsnt 1-4 # - is Tis

 <Desc / Clms Page number 4>

 structural part of the polyurethane, thus forming, with the latter, a strong chemical bond, while avoiding the weak flame-retardant properties, which are usually found in polyurethanes, in particular, ion polyurethane transformed into foam, while avoiding also the loss of these flame retardant properties in foamed polyurethanes treated with an additional flame retardant composition.



   Another feature of the present invention consists in developing a flame retardant, self-extinguishing, solid, semi-solid or flexible cellular polyurethane.



   A characteristic feature of the present invention is to prepare a flame retardant polyurethane foam of light weight, but substantially strong and used for several applications including flame retardant panels for structures such as airplanes, buildings, etc.



   It has been found that by replacing all or part of the usual active hydrogen compound, such as for example a polyol, currently used in the preparation of polyurethane foams, by a phosphorus compound, the molecule of which contains at least 2 atoms of active hydrogen, in particular the product of an acid of phosphorus, of which the. molecule contains at least 2 hydroxyl groups, together with an alkylene oxide, the flame retardant degree of the finished product was remarkably improved. The flame retardant degree depends on the amount of the phosphorus compound used.

   If the amount decreases, the flame retardant degree also decreases, but a better flame retardant property is obtained when even an amount as small as 5% of the phosphorus-containing compound is used to replace 5% of the usual polyol, the replacement being carried out on the basis of active hydrogen equivalents.



   As stated above, the phosphorus compounds used according to the present invention are those containing at least 2 active hydrogen atoms per molecule. There are many types of chemical structures containing active hydrogen and it is understood that all of these types are within the scope of the present invention.

   As non-limiting examples of active hydrogen radicals, which can be associated with phosphorus in an organic chemical compound, there are:

 <Desc / Clms Page number 5>

 
 EMI5.1
 
 EMI5.2
 where -R- represents an aloylene or Mylene radical or else a series of alkylene or az7lènel radicals, can be separated by hetero atoms, such as ors and 3, for example -CH2CH20CH2CH20CH2 :: i-, -C6'B. -C6'fJ ..-, c6E-e-0-17 or input, linked
 EMI5.3
 to a phosphorus atom, directly one by oxygen, sulfur or nitrogen,
 EMI5.4
 R 'representing an alkyl * or aryl radical is still 1'% bmW *
 EMI5.5
 Among the most useful compounds, containing phosphorus, are the
 EMI5.6
 compound containing hydroaqrlea groups providing active hydrogen.

   Among oe. compound, it is envisfflp according to the present inventions the use of gold compounds
 EMI5.7
 ganic and inorganic phosphorus, usually containing 2 hydroxyl groups.
 EMI5.8
 are the aiecu identified by the number of active hydrogen atoms present.



  1 - Compound containing 2 atoms of active hydrogen per molecule.
 EMI5.9
 



  1 - inor6aniqpoS 0 a) phosphorous acid * 110-î-il OR * II- organic * N a) 1IODOe8'ters of phosphoric acid 80 - OH * on * 0 b) acid * phosphonics 8OR *
 EMI5.10
 c) pjrOphoaphor1qu8 acid dienters
 EMI5.11
 
 EMI5.12
 d) sulfuric acids
 EMI5.13
 

 <Desc / Clms Page number 6>

 
 EMI6.1
 
 EMI6.2
 e) dilate of diphosphoric acids
 EMI6.3
 
 EMI6.4
 f) dienters diacids diphosphonic
 EMI6.5
 
 EMI6.6
 S) an oxide or b1ox adduct; alkylene rde of either of the compounds shown in .1-I- (a) and 1-II- (a-t), loxde dalkylene being 82-C-C8-8 ", where B" represents 99 C83, c2H5 and C1IlJ1.



  In the formats 01-4..8 \ 18 .. represents a rad10al 8100.71. or substituted or unsubstituted aryl, while R 1 represents an aloo, r1ene or arylene radical or alternatively a series of aloylene or a171 radicals. which can be separated by hetero trumps, oosae for example 09 Y and S, for example - # 2cJJIr2CHl) CJI2 # 2- '-C6H4-C6H4-' -f: 6H4OC6H4- or others. the "*" denotes active hydrogen * 3 - C08p08eS. containing more than 2 active hydrogen assets per molecule.
 EMI6.7
 



  1 - i% JorganiqU88 Si a) phosphoric acid HO-P OE * OR * b) py pho "h ic acid * HO 0 0 OR * z * HO /" \ OH *
 EMI6.8
 o) polyphosphonic acids, eg oomae tripolnhoephorlque acid.
 EMI6.9
 



  II - organic
 EMI6.10
 a) mmoesters of pyrophoaphoric acid
 EMI6.11
 
 EMI6.12
 b) diphosphonic acids
 EMI6.13
 

 <Desc / Clms Page number 7>

 
 EMI7.1
 c) lI.ono8eters of diphoa honic acids
 EMI7.2
 
 EMI7.3
 d) Ohhosfioriqnos acids
 EMI7.4
 
 EMI7.5
 e) IDOn08stera of diphoaphoric acids
 EMI7.6
 
 EMI7.7
 f) the product of en aycol, !! OR'OR, having reacted svea P2o5. g) the product of a pdydycol, X (0R '10E, reacted with P2058 h) the product of an 8long of a glycol or a polyglycol and an alcohol, RM9 reacted with P2058 1) the product of 'nn c0llp08é po1J having reacted with P205. j) an O3 [yda or alkyleno dioxide adduct of any of the compounds shown in 1-I- (sc) and 1-II- (a-1), exyde 49alkylene being HC-CH-R ", where R represents H, CHC-BL and 011201.

   
 EMI7.8
 k) one or the other of the products represented in 1-II (g) and
 EMI7.9
 B-II- (3), reacted with? 205.



  1) one or the other of the products represented in 1-IT (k), having reacted with an oxide or a dtalcoylèneg dioxide, represent, by O: # - R '"where" R "represents H, Cl11,12, and CH2C '!, Daas fumule8 c1-4e88118, R represents an alkyl or arylene radical or a series of aloylene or arylene radicals, which can be separated by hetero atoms such as 0, 1l and S; such as for example -OEàOE2oOE2M2oC " 2 = 273, -06H4C6H4- '6HlC6H4-' or others, while x represents a eut-ter number
 EMI7.10
 positive.

   The "*" indicates active hydrogen.

 <Desc / Clms Page number 8>

 among the many compounds represented above in A and B and among the preferred organic compounds of phosphorus, whose molecule contains at least 2 active hydrogen atoms and which can react with polyisocyanates, it has the reaction products of oxides of alcoholic acid and phosphoric acid as well as the reaction products of dialkyl-pyrophosphoric acids and dialkylen oxide.



   According to the present invention, an organic phosphorus compound, the molecule of which contains at least 2 active hydrogen atoms, or a mixture of this compound and the polyol normally used, is mixed with an aromatic diisocyanate, such as, for example, diiscocyanate of tolylene and the mixture is heated to form a prepolymer. To obtain the foamed product, there is in the mixture an excess of about 5 to 40% of diisocyanate, calculated on the unreacted NCO. The mixture is then treated with a catalyst, a surfactant, a product containing additional phosphorus and / or the usual polyol as well as water or an inert low boiling liquid, such as for example a chloroflucrocarbon, that is to say one of the Freons.

   The production of foam takes place and the product is treated at a temperature of 25 to 100 C for a period varying between about 10 minutes and 2 hours. A light, white cellular material is formed.



   For the purpose of the present invention, the phosphorus acid must contain at least 2 hydroxyl groups per molecule. If there are less than 2 groups, the crosslinking and the formation of the polymer is not facilitated. When employing a bifunctional phosphorus compound, it has been found that the best flame retardant properties are obtained by employing about 5 to 70% of the phosphorus compound as a replacement for the usual active hydrogen compound. When the phosphorus compound is trifunctional or has a higher function, in order to obtain the best practical flame retardant property, about 30 to 100% of the usual active hydrogen compound can be replaced by the phosphorus-containing compound.



  However, in both cases, acceptable flame retardant properties for certain applications can be obtained by using the phosphorus compounds in amounts greater or less than the percentages indicated above. The polyisocyanates used are those well known in the art for forming conventional polyurethanes and it is not necessary to give a detailed description thereof.

 <Desc / Clms Page number 9>

 



   The following examples illustrate the present invention and it is understood that they in no way limit it.
EXAMPLE I
 EMI9.1
 solid foam prepared with: w1r of tolylene diisooyanate and phosphoric acid 'D1' Opoxyl. flation of Freon.



  (a) Format of the prepolymer 300 gr. p = po2ylated phosphoric acid, prepared in accordance with US Pat. No. 2,372,244 and having a hydroxyl number of about 365, and 672.8 gr. of tolylene aocyanate (80% of 2,4tolylene diiaooyanate and 20 of 2.6-% olylene diisocyanate) in a 1000 111 flask fitted with a stirrer. tor and a therm # eter. The mixture was covered with nitrogen, to avoid IthUII: I.d1-
 EMI9.2
 you. While stirring, the temperature was brought to 90 ° C. and kept at 3 ° C. for a period of * hour, then cooled to 258 C. The product was a pale yellow liquid, containing 25 ° C. 04 of unreacted NCO groups (calculated on the total weight of the mixture). The viscosity of the liquid was 3200 oentipoise at 23 C.
 EMI9.3
 



  (b) Training of 1IOU88e ..



  1 50 gr. of the product of (su in a stainless steel beaker of 400 garlic was added 45.3 gr, (8toichiometric equivalent of residual 1fCO) of the propoxylated phosphoric acid of (a). Was added, to the mixture, 14, 2 gr. Of CC13F reon 11 from du Pont, and 0.5 gr. Of an organoailicone block polymer anirtaotant, corresponding to the formula
 EMI9.4
 
 EMI9.5
 where H and Lis are methyl groups, El is ethyl, p, q and r have an average value of 3, while the unit (CnJ1.2; D.) o ;. represents a block of polyoxyethylene, containing on average 16 dfoxyethylene units, z being equal to 16 and n -2; then all the products are thoroughly mixed. During the mixing operation, we lost a little Freon and we had to replace it.

   After mixing, 0.5 ml of dibutyl tin dilaurate catalyst was added, stirred ra-
 EMI9.6
 pidempnt the mixture for 15-20 seconds s t we poured all the products

 <Desc / Clms Page number 10>

 in a 15.24 x 15.24 x 10.16 cn carton coated with a commercial parquet wax (paste) * Foam formation began immediately. The foaming mixture was placed in a maintained oven at 470. C. The maximum foam height was reached about 30 seconds after the mixture was poured into the carton. The foam became non-sticky after 5 minutes and reached its final strength after 10 minutes. at 70 ° C. The foam was removed from the oven after reaching this final strength and poured out of the carton.



   EXAMPLE II
 EMI10.1
 Solid foam, prepared * from tolTlene dibooyanate, propoxylated phosphoric acid and a regular polyol. Insufflation of Fréen.
 EMI10.2
 



  (a) Formation of the "01'éDOIYJ1st.



  We placed 300 gr. of propozylated phosphoric acid and 57.0 gr. of Tolyléns diieoo1'anate in a 2 L flask fitted with a thermometer and a stirrer. Nitrogen was used to cover the reagents in order to avoid humidity. While stirring, the temperature of the mixture was brought to 1006 ° C. and maintained for 1 hour. After this heating period, 0.034% unreacted ICO group remained. We ¯a $ orU 970.0 gr. of additional 10011'-lene diisocyanate and the temperature of the mixture was lowered to about 60 ° C.



  The temperature was raised to 700 ° C. and stirring continued for an hour at this temperature. Then the product was cooled to about 25 C. The product
 EMI10.3
 was a pale yellow liquid, containing 31.1J6 unreacted NICO groups and having a viscosity of 600 centipoise at 20 C.



   (b) Formation of foam.



   One was prepared by the same method as that indicated in Example 1 (b). The quantities of the materials used were as follows: 50 gr.
 EMI10.4
 of the prepolyere of II (a), 317 gr. of propoxylated phosphoric acid, 22 gr. of a commercial triol based on polyether and having a hydroxyl number of approximately 378, 15.6 gr. of Freon-11, 0.6 gr. of dibutyl tin dilaurate and 0.6 gr. of
 EMI10.5
 turfaotant defined in I (b).



  Among the well-known polyether-based polyols which can be used to form polyUretane8 is the "p'iax Triol 'V-3 & 0" from Union

 <Desc / Clms Page number 11>

 
 EMI11.1
 Carbide (polyether-based commercial triol defined in II (b)), the "Atlas c-2qu0" (required addition of Ta ± to propylene to sorbitol having a hydroxyl number of about 490) and the "Pluraool TP-440" from Iryandotte (add product of propylene oxide to trimethylolpropanep having a hydroxyl number of about
 EMI11.2
 380). EXAMPLE
 EMI11.3
 solid foam prepared from tolylene aocyaaate,
 EMI11.4
 propoxylated phosphoric acid and an ordinary polyol. insufflation of Freon *
 EMI11.5
 (a) lroacaation of oréoo1Ynére.



  The propolper of Example II (a) was used.
 EMI11.6
 



  (b) Formation of foam.



  The mousse was prepared as indicated in Example I (b), with this
 EMI11.7
 exception that we only used 9 # 9 gr. propoiy3é phosphoric diacid, the remainder of active hydrogen being provided by 4.0%. of the conventional triol of Example II (b). In addition, the Freon content was brought to 15.6 g., The dibutyl tin dilavrata to 0.6 ml and the surfactant to 0.6 g.



  Xou e solid prepared from tolylene diisooyanate and ordinary polyel. 3reon insufflation.



  (a) Formation of the prepolvzere.



  50 ger were placed. of the triol of Example II (b) and 342.0 gr. of tolylene diisocyanate (80} 6 of 2,4-jolylene diiooeyanate and 2J% of 2p6-tolylene diisocyanate) in a 2000 ml talion, stirred with a stirrer, a tea> our
 EMI11.8
 and an apparatus for covering the mixture under a nitrogen atmosphere. We acted
 EMI11.9
 the mixture and the reaction temperature was brought to 70 ° C. 50 g. of additional triol and the temperature was raised to "900 C". The mixture was heated to 900 C for 30 minutes, then cooled to 50 "C, before storage. The product was a pale yellow liquid, containing 30.336 unreacted NCO groups, this liquid having a viscosity of 8W centipoise at 25 "C.



  (b) Foam formation 47 6 ** of the above prepolymer, 50 gr. triol; 0; 6n gr. of the silicone surfactant of Example I (b) and 20.5 gr, Freon (CCI3F) in a

 <Desc / Clms Page number 12>

 400 ml stainless steel beaker and stirred vigorously.



  Some of the Freon had to be replaced, due to loss during mixing. We have placed 0.6 gr. of dibutyl tin dilaurate catalyst into the mixture and stirred for 10-20 seconds. The foam formed almost immediately and the foaming mixture was placed in a 15.24 x 15.24 x 10.16 cm carton, coated with a commercial paste wax for floors.



  The carton, containing the foaming mixture, was placed in an oven at 70 ° C. for 10 minutes. The foam became non-sticky in less than a minute and had reached almost full strength in 2-3 minutes, at a temperature of 70 ° C.



   EXAMPLE J V
Solid foams prepared from tolylene diisocyanate and an ordinary polyol, from tolylene diisocyanates and propoxylated phosphoric acid or from tolylene diisocyanate, ordinary polyol and propoxylated phosphoric acid.



   Insufflation of Freon, (a) Formation of the prepolymer, (1) 300 g were mixed. of phosphoric acid propoxylated with 668.5 gr. diisocyannte they tolylene and the mixture was heated at 90 C for ¸ hour.



  The entire reaction was carried out under nitrogen protection. At the end of the heating period, the mixture was allowed to cool to room temperature.



  The product had a viscosity of 3340 oentipoise at 21 ° C and the amount of unreacted NCO groups was 25.06%.



   (2) 300 g were mixed. of propoxylated trimethylolpropane, having a hydroxyl number of 373 (see example II (b)), with 682 gr. of tolylene diisocyanate and the mixture was heated at 90 ° C for hour. The entire reaction was carried out under nitrogen protection. At the end of the heating period, the mixture was allowed to cool to room temperature. The product had a viscosity of va centipoise at 25 ° C and the amount of unreacted NCO groups was 24.7%.



   (b) Preparation of mousse,
4 different foams were prepared from the prepolymers L and 2

 <Desc / Clms Page number 13>

 above. These foams were obtained by mixing the ingredients shown in the table below, the dibutyl tin dilaurate catalyst being added last. The mixture of ingredients was stirred for 15-20 seconds, then poured into a 12.7 x 12.7 x 10.16 oz coated paper container * This container was placed in an oven at 50 ° C. and it was cooked. The foams had a density of 0.0448 to 0.0464 kg / liter.
 EMI13.1
 



  Composi tion of US, SU. Sl N-3 N * 4 g. prepolyere 1 - - - 50.0 g. prepo7.rsire 2 50.0 50.0 50.0 g,! 13PO4 proporlated - 183.2 bzz 46j. 3 g,% rimethylolpropane hair (see example II (b)) 44.2 26.7 9.2 g. poly (diaetl-Gil1cone) DC-200 of Example XI (o) 0.5 0.5 0.5 0.5 g. ccl3g (Freon) 14.4 4a4 14.4 14.4 g. Dibntyl tin dilaurate 0.4 0.4 0.4 0.4 EXAMPLE JJ Preparation of solid foams from ordinary polyester polyols and polyols.



  (a) Pre'P01] '] l.



  Lo prepolymers used in the following preparations of foams, was the reaction product obtained by reacting, for about 1 hour
 EMI13.2
 at 70-90 ° C we have an atmosphere of nitrogen, 80 parts of 4118OO78n &: 1 :. of tolylene with about 20 parts of a polyester polyol of the pbtal1que-aMpic type (such as, for example, "3eleotron 6002" from the Pittsburgh Plate Clsss CoapaD7), having a hydroxyl number of 438. The prepo7.3rmer contained an excess of 30 .5 $ 6 unreacted NCO groups.
 EMI13.3
 



  (b) FQ, foam raaition.



  (1) A polyester-based control foam was prepared by placing 50 gr. of prepolymer (VI-a) 48.5 gr. 1 t eyemp * - polyester polyol, VI (a), 0.4 gr. of the silicone surfactant of Example I (b) and 17.0 gr. of Freon-11 in a spade '? 400 ml stainless steel. After stirring vigorously for 10-15 seconds, the loss of Freon-11, due to evaporation, was replaced,

 <Desc / Clms Page number 14>

 0.25 g were added. of triethylamine and stirred vigorously for 10-15 seconds. All the product was poured into a 15.24 x 15.24 x 10.16 cm. Carton, coated with a commercial paste wax.

   The mousse was immediately placed in an oven preheated to 40-50 ° C and held at that temperature until it had almost reached its final strength (5-10 minutes).



   (2) Another mousse was prepared exactly as described above,
 EMI14.1
 with this exception that we used 12.0 gr. of propoxylated dibutyl-pyrophoephoric acid (see Example XI (a)) and 41.2 gr. polyester polyol of Example VI (a) above.
 EMI14.2
 



  BXP2 # LB TI;!; solid foam prepared from tolylene dii800yanate and phosphoric acid proposyli. Insufflation of C020 (a) Formation of 'Dré' D01nre.



  The prepolymer of Example II (a) was used.



  (b) Foam formation, A 66.0 gr. of the above procedure, in a 400 al stainless steel beoher, 41.0 gr. of propoxylate phosphoric acid, 2.0 ml of water and 0, were added. 7 µl of the silicones excess of Example I (b) The mixture was stirred vigorously and 0.82 µl of 1f-: utborphollne was added, Then the products were mixed rapidly for 10-20 seconds. We poured the mixture into
 EMI14.3
 a 15.24 x 15.24 x 10.16 cap carton coated with ordinary wax and placed in a tower, maintained at 95 ° C. Maximum growth was reached in 2-3 minutes. The foam became non-sticky in about 15 minutes and was still somewhat soft after 30 minutes at 95 ° C.

   We then have
 EMI14.4
 the foam was removed from the oven and its strength increased rapidly upon cooling.1se- ment to room temperature.
 EMI14.5
 



  EX1iXPLB VII! Nouas-) solid prepared from tolylene diisocyanate, propoxylated phosphoric acid and an ordinary polyol. CO2 blowing.
 EMI14.6
 (a) Formation of the prepolymer. The prepolymer of Example II (a) was used.

 <Desc / Clms Page number 15>

 



   (b) Formation of foam;
We prepared the. foam exactly as described in Example VII (b), with the following exceptions *: the polyols used were propoxylated phosphoric acid (23.7 gr) and the ordinary triol of Example II (b) (16.8 gr.). The
 EMI15.1
 foam became non-sticking in 10 minutes.



  EOMPU! IX solid foam, prepared from tolylene dioocyanate, propoxylated phosphoric acid and an ordinary polyol. CO2 blowing.
 EMI15.2
 



  (a) rnat3oa of vrepo -9.



  The prepolymer of Example II (a) was used.



  (b) 1'o1 "ll & \ 1on d. 1IOU., ...



   The foam was prepared exactly as described in Example VII (b), with the following exceptions the polyol * used were propoxylated phoaphoric acid (4.8 g) and the usual triol (33.3 g). The rise became non-stick in 5 minutes and maximum strength was reached in 20 minutes at 95 ° C. without removing it from the oven.



   EXAMPLE X
 EMI15.3
 .or ... solid prepared from to7arlèae diieoeyanate and an ordinary polyol. Insufflation of CO2. c) fbxxatioa of the LiLepolymer, The prepolymer of Example II (a) was used.



  (b) 191't18t1on of aouese.



  1 66.0 gr. of the prepolymer, contained in a beaker of 400 Ill. of stainless steel, 35.0 gr. of the ordinary triol of Example II (b), 0.07 al
 EMI15.4
 of the surfactant of Example I (b) and 2.0 gr. of water. The products were mixed with stirring and 0.82 µl of N-methyl orholins catalyst added. The mixture was stirred quickly and foaming began immediately. The ingredients were transferred from the beaker into a 15.24 x cira coated carton.
 EMI15.5
 15.24 x 10.16 cm. The mousse was baked in an oven at 90 ° C for 30 ... 1 ... nutes.



   The foams prepared in each of the above examples were subjected to the following test for their flame retardant properties.



   A 32.25 cm2 and 1.27 cm foam block was placed horizontally

 <Desc / Clms Page number 16>

 thick on a 7.62 cm ring clamp. Underneath the test tube a small Bunsen burner, having a 6.35 cm flame, was placed so that the tip of the flame just touched the center of the bottom of the test tube. The burner was kept in this position, until the flame passed through the top of the foam. Then the burner was immediately removed. The time taken to cross the wese was noted, the time that the foam continued to burn after removing the burner, and the time required to completely burn the foam up to the ring clamp, as long as it did not sink. be extinguished before reaching oelle-oi.

   If the specimen self-extinguished in 5 seconds or less, the burner flame was reapplied for an additional 5 seconds and the additional burn time noted. The results are shown in Table I.



   Table I
Mousse puffs with Freon
 EMI16.1
 
<tb>
<tb> Example <SEP> Duration <SEP> for <SEP> Auto- <SEP> Burée <SEP> of <SEP> comp <SEP> Dnrée <SEP> of <SEP> Darée <SEP> of
<tb> cross <SEP> the <SEP> fire extinguisher <SEP> bastion <SEP> until <SEP> combustion <SEP> combustion
<tb> foam <SEP> to <SEP> the ring <SEP> before <SEP> auto- <SEP> until
<tb> ¯¯¯¯¯¯¯¯ <SEP> ¯¯¯¯¯¯¯ <SEP> ¯¯¯¯¯¯¯¯¯¯ <SEP> extinction <SEP> re-ignition
<tb> I <SEP> 12 <SEP> sec. <SEP> yes <SEP> - <SEP> 2 <SEP> sec. <SEP> 1.5 <SEP> sec.
<tb>



  II <SEP> 12 <SEP> seo, <SEP> no <SEP> 45 <SEP> sec. <SEP> - <SEP> -III <SEP> 13 <SEP> seo. <SEP> no <SEP> 36 <SEP> sec. <SEP> - <SEP> -Control
<tb> IV <SEP> 8 <SEP> sec. <SEP> no <SEP> 25 <SEP> sec. <SEP> Control
<tb> V-1 <SEP> 14 <SEP> sec. <SEP> no <SEP> 30 <SEP> sec. <SEP> - <SEP> -V-2 <SEP> 13 <SEP> sec. <SEP> no <SEP> 35 <SEP> sec. <SEP> - <SEP> -V-3 <SEP> 10 <SEP> sec. <SEP> yes <SEP> - <SEP> 45 <SEP> sec. <SEP> -V-4 <SEP> 13 <SEP> sec. <SEP> yes <SEP> - <SEP> 28 <SEP> sec. <SEP> -Control
<tb> VI-1 <SEP> 14 <SEP> sec. <SEP> no <SEP> 45 <SEP> sec. <SEP> VI-2 <SEP> 17 <SEP> sec. <SEP> yes <SEP> - <SEP> 44 <SEP> sec.

   <SEP> -
<tb>
 

 <Desc / Clms Page number 17>

 CO2 blown foams
 EMI17.1
 
<tb>
<tb> Example <SEP> Duration <SEP> for <SEP> Auto- <SEP> - <SEP> Duration <SEP> of <SEP> cm- <SEP> Duration <SEP> of <SEP> Duration <SEP> of
<tb> cross <SEP> the <SEP> extinguisher <SEP> bustion <SEP> jasqu '<SEP> combustion <SEP> combustion
<tb> foam <SEP> to <SEP> the ring <SEP> before <SEP> auto = <SEP> until
<tb> ¯¯¯¯¯¯¯ <SEP> ¯¯¯¯¯¯¯, ¯¯¯¯¯¯¯¯ <SEP> extinction <SEP> re-ignition
<tb> VII <SEP> 8 <SEP> sec. <SEP> yes <SEP> - <SEP> 4 <SEP> sec. <SEP> 2 <SEP> seo.
<tb>



  VIII <SEP> 8 <SEP> seo. <SEP> yes <SEP> - <SEP> 17 <SEP> sec. <SEP> -IX <SEP> 12 <SEP> sec. <SEP> no <SEP> 85 <SEP> sec. <SEP> - <SEP> -Control
<tb> X <SEP> 7 <SEP> sec. <SEP> no <SEP> 30 <SEP> noce <SEP> - <SEP> -
<tb>
 
From the above table, it can be seen that the foams not containing the phosphorus reaction product burned easily inside the ring.

   The foams of Examples I, V-4 and VII, containing none of the usual polyols, but only the propoxylated phosphoric acid, did not burn to the ring and were self-extinguishing. After being crossed by the flame, the foams of Examples I and VII only burned for 2 and 4 seconds respectively and, when re-ignited, they burned 1-¸ and 2 seconds respectively.



  With regard to the foams of the other examples, where some part of the ordinary polyol was replaced by propoxylated phosphoric acid, a remarkable improvement was observed compared to control samples IV, V-1, V1-1 and X, which burned completely to the edge of the ring in 30 seconds or less.



   Flame retardant foams have also been prepared from other alkoxylated phosphoric acids, such as, for example, ethoxylated phosphoric acid.



   EXAMPLE XI
Soft foam, prepared from toylene diisocyanate, ordinary polyols and propoxylated dibutyl pvrophosphoric acid, (a) Preparation of porpoxylated dibutyl pyrophosphoric acid.



   Over a period of 2.5 hours, 426 gr was slowly added. from P205 to 444.7 gr. butyl alcohol. The alcohol was stirred during the addition and the temperature was kept below 15 ° C. When the addition was complete, the external cooling was removed and the temperature raised to 35-40. * C in about two hours. Stirring was stopped after four hours and the product was allowed to stand overnight at room temperature. We

 <Desc / Clms Page number 18>

   then heated it for two hours at 70 C.

   We obtained 863 gr. of product
 EMI18.1
 acid, having a primary acidity of 5.98 equivalents / molecular / gr. and a total acidity of 7.17 equivalents / molecular / gr.
 EMI18.2
 At 420 em. From the above product, propylene oxide was added dropwise, while stirring the mixture at a temperature of 35-45 C. When all the oxide had reacted, the excess oxide was removed and 805 g were obtained. propoxylated dibutyl-pyrophosphoric acid. This product was found to have a hydroxyl number of about 210.
 EMI18.3
 



  (b) Yo1'l1fot1on of ppol = nMt1 "8.



   In a nitrogen atmosphere, 34.1 g were mixed. propoxylated dibatylpyrophosphoric acid, 91.9 gr. a tetratunctional hydroxyl compound,
 EMI18.4
 sold under the brand name "T.tron1c 701" by the Yandotte Chemicale Corp., and 237.5 gr. polypropylene glycol (IT6 2025 from Union Carbide Corp.). g this mixture was added 80.6 gr. of tolylene dilsocyanate (80% of 2.4- and 20% of 2.6-). The mixture was stirred, heated to 1000 C and kept at that temperature for two hours. The temperature was then lowered to 60 ° C. and 63.7 g were added. additional tolylene diisocyanate. The mixture was stirred for 15-20 minutes and poured from the reaction vessel.

   The
 EMI18.5
 life at 239 C was 4,200 centipoise and the percentage of unreacted NCO gronpea was 8.7%.



    The "ftronic 701" responds to the following formula:
 EMI18.6
 (H (C2H40) y ia3H6o) =) 2 - "-C" 2-CI'2 - "- (CH60) x (C2H40) yH) 2 where y is about 6 and x, about 12.



   (c) Foam formation
We mixed 60 gr. of the above prepolymer with 1.4 gr. of water, 0.3 gr of dimethyl silicone (DC 200, product of Dov Corning Corp., having an indi-
 EMI18.7
 this viscosity of 50 oentipoises at 25 ° C.), 0.6 gr. of N-meObylmorpholme and 0.18 gr. of trime thylamine. The foaming mixture was placed in an oven at 700 ° C for 25 minutes. It was then cooked in. 121 C for 3 hours, to form a flexible cellular polyurethane.



   EXAMPLE XII
 EMI18.8
 Foam !! Hem, -: r4-, made from kiiôvv, âûcv tv of ordinary tolyiéiac and dô polyols.

 <Desc / Clms Page number 19>

 



   A control foam was prepared exactly as described in Example XI, with the exception that the prepolymer was prepared using 600 gr. of PPG 2025, 200 gr. of Tetronic 701, 124.6 gr. of tolylene diisocyanate for the first addition and 171.8 gr. of, tolylene diisocyanate for. second addition. The content of unreacted NCO groups was 9.10% and the visco-
 EMI19.1
 The temperature at 17 ° C was 6,800 centipoisene. The products of Examples XI and XII were then tested to determine their combustion properties. A 1.27 cm x 2.54 cm x 15.24 cm sample strip was placed in a clamp at an angle of 45.



  A flame was applied to the lower end and the time taken to burn 10.16 cm of the strip noted. The material not containing the phosphorus compound (Example XII) burned over 10.16 cm in 39 seconds * The material obtained with the phosphorus compound (Example XI) was self-extinguishing, i.e. 'By removing the applied flame, the tape stopped burning.



   EXAMPLE XIII
Preparation of films and coatings using dibutyl acid
 EMI19.2
 -nY% 'O> b08J> boI'ioue 1> ro \) oplé and ordinary Dolyols, -
Films and coatings were prepared on wax paper, employing the following compositions: Formula N 1
 EMI19.3
 P - epolymer of Example IV (a) 5 gr.



  Triol of Example II (b) 2 gr. propoxylated dibntyl-pyrophoaphoric acid 6 gr. Dibutyl tin dilaurate 0.16 ml.
 EMI19.4
 



  Formula N * 2> repo1yllére of Example Ilt (a) 5 gr.



   Triol of Example II (b) 2 gr.



     Polypropylene..glycol 475 (Union Carbide) 4.7 gr.



   Dibutyl tin dilaurate 0.16 ml.



   In both cases, the polyoles and prepolymers were mixed together, stirred, and then the catalyst was added. After thoroughly mixing, a film was cast onto ordinary waxed paper, using a blade of

 <Desc / Clms Page number 20>

 raclette. The paper and film were placed in an oven preheated to 40-45 C.



  The product of formula N 1 became tack-free in about 30 minutes and that of formula N 2 in about 15 minutes. After a 30 minute stay in the oven at 40-45 ° C, the samples were removed and kept at room temperature for one hour. The films were about 0.381mm.



   The flame properties were noted as indicated below
A sample of each specimen was tested as 1) a coating and 2) as a film
For the coating form test, a test piece was prepared by cutting a 2.54 cm x 20.32 cm strip (coating size), with a 1.27 cm wide strip of black paper remaining attached to a strip. longitudinal edge of the control strip. The tape was hung vertically and the flame was applied to the paper on the bottom corner of the tape.



   For the film test, a 2.54 cm x 25.4 cm strip was cut and the wax paper was completely removed. A 5.04 cm x 2.54 cm strip of waxed paper was pressed onto one end of the film strip so that 3.81 cm of the paper protruded from the strip. The tape was hung vertically and the flame applied to the protruding paper.



   In the coating test, the product of formula N 1 simply burned the 1.27 cm waxed paper strip and as soon as the coated area was reached it immediately extinguished. No flame was noticed after 12 seconds. The coating only severely burned for about 0.317 cm with some discoloration noted up to about 0.634 cm in the vertical edge. On the other hand, when the paper was consumed, the product of formula N 2 continued to burn up to about 1.27 cm from the vertical edge. At this point, the z8ne, where the support wire was attached, burned (27 seconds) and the test piece had + dropped.

   It continued to burn and went out after burning for about 1 minute, when the fallen sample was found to be completely consumed.



   In the film test, the product of formula N 1 burned for 2 seconds. At this point, the paper was burnt and the heat generated melted the film. Several flaming drops fell, but did not

 <Desc / Clms Page number 21>

 continued to burn. AT the same time, the test specimens disappeared. In all the procedures, a self-extinction time of 3 seconds was obtained from the moment the paper was ignited. On the other hand, the product of formula N 2 a burns for 27 seconds and after this time the entire specimen was consumed except about 1.27 cm from the top.

   During the combustion, molten drops in flames fell and continued to burn completely (several minutes).



   WINE EXAMPLE
Preparation of films and coatings, using propoxylated dibutylpyrophosphoric acid and ordinary polyols.



   Filas 0.381 cm thick of the two formulas below were poured onto waxed paper and placed in an oven at 40 ° C, until they became non-sticky (about 25 minutes). The ingredients were mixed (catalyst added last), then spread out on the paper with a squeegee blade. After baking, films were obtained by removing the waxed paper.



   The products were as follows:
N 1 N 2 g. prepolymer (see V (a) (2)) 25.0 25.0 g. propoxylated trimethylolpropane 7.5 7.5 g. propoxylated dibutyl-pyrophospboric acid - 27.0 g. polypropylene glycol 425 22.0 g. Dibutyl state dilaurate 1.0 1.0
The coatings and the detached films were subjected to the flame as described in Example XIII above.



   The results were as follows:
N 1 - completely grinds in both trials. Film burning time 24 seconds. Burning time of the coating!
21 assist
# 2 - Self-extinguished as soon as the ignition paper on the film was consumed. Only 1.27 cm of the film was attacked by fire. The film burned for 5 seconds and went out 2 seconds after removing the flame.

 <Desc / Clms Page number 22>

 



   In the coating test, the vertical edge was attacked by fire over 0.317 cm. No trace of combustion was noticed beyond the coated area.
 EMI22.1
 



  EXAMPLE XV Preparation of a thermosetting molding material from isocyanate with phosthetic and ordinary polyols.



   Two 2.54 x 2.54 x 20.32 cm molded articles were prepared according to the following two formulas,
 EMI22.2
 ioz 1 Prepolymer of Example I (a) 100 gr. Triol of Example II (b) 88 gr.
 EMI22.3
 



  Tin dibu't7l1qU8 dilaurate 0.5 gr. N-2 n6pOlywéte formula of Example I (a) 100 ger.



  Proportional phosphoric acid: J "le 90.6 gr.



  Dibutyl tin dilacarate 0.5 gr.



  In both cases, the quantity. to this product. oi-deaaus were mixed 1ntil: uent (catalyst added last) in a 400 ml beaker. Stainless steel. About 30 seconds after the addition of the catalyst, the temperature of the product started to rise to high and was applied to a 2.54 x 2.54 x 20.32 cm sheet of paper (coated with wax. ordinary for parquet a). In about 5 minutes, the product has solidified enough to retain its unsupported shape. Heat development continued at an accelerated rate for about 10-15 minutes, then gradual cooling occurred.

   As the cooling proceeded, the hardness of the sample gradually increased. No external heat has been applied.



   About 4 hours after pouring the samples, several cutouts from each bloo (1.27 x 0.317 x 15.24 cm) were taken. The flame properties were determined by placing a sample of each formula in a horizontal position and holding it in that position with a pin at one end. From the free ends of each 1.27 x 0.317 x 15.24 cm sample, the inscriptions 2.54 and 12.7 cm were marked,

 <Desc / Clms Page number 23>

 
The product of formula N 1 was ignited. using a small Bunsen burner (flame of about 5.08 in), held on the free end for 5 seconds, at an angle of 45.

   The test tube was ignited and continued to burn. : As soon as the flame reached the first mark (2.54 cm from the free end), the combustion speed was noted. The flame reached the second mark (10.16 cm of burnt material) in 4 minutes 35 seconds. From then on, the burning rate was approximately 1 minute, 9 seconds * per 2.54 cm.
 EMI23.1
 A sample of formula 2 (agn dimension 1.2T x 0.317 x 15.24 cm) was treated in the same manner as N 1. The test piece was extinguished.
 EMI23.2
 of itself during 3 successive 5 second ignitions. Then the flame was kept on the test piece until it reached the mark of f 2.54 cm.

   At this point, the flame was removed and the test piece self-healing within 7 seconds. The test piece was re-ignited in three successive periods of
 EMI23.3
 30 seconds. In each case, the test piece is extinguished by itself, on average, in about 4 seconds. Each reagent was applied immediately after the flame of the previous one had disappeared.



  TEMPLE XVI Preparation of thermosetting mold material from i8QQyanate .. with pho.'Phatiaue8 and Ord1na1re8 polyols.



  Three molded articles were prepared from ptepolyké> 8 Y (a) (1) and V (a) (2). They were obtained by mixing the ingredients shown in the table below (catalyst added last) and pouring the stirred mixture into a mold. Each article hardened in about 3 minutes at room temperature.



     Compositions of molded articles.
 EMI23.4
 



  N * 1 N * 2 N *? g. prepolymer (see q (a) (1)) - - 100.0 g. prepol18ere (see V (a) (2 100.0 100.0 - g. H3PO4 propoxylated - 60.7 92.8 g. trimethylolpropane propoxylated (see IIb) 87.4 30.0 g. dibutyl tin dilaurate 0, 3 0.3 0.3
The above items were flame tested as described in the method of Example XII above.

 <Desc / Clms Page number 24>

 



   # 1 - Lit for 5 seconds and continued to burn after removing flame. 10.16 cm burnt in 3 minutes, 42 seconds.



   Drops continued to burn after falling from the test tube.



   N 2 - Passed out on its own. Flame maintained on the test * successively for periods of 5, 5, 10, 30, 30, 30 and 30 seconds with extinction times of more than 1, more than 1, more than 1, 5, 25, 19 and 44 seconds respectively.



   The drops did not burn.



   N 3 - Passed out on its own. Flame maintained on the test piece successively for periods of 5, 5, 10, 30, 30 and
30 seconds with extinction times of more than 1, more than 1, more than 1, 1.1, 1 and 2 seconds respectively. The drops did not burn.



   Cellular or solid flame retardants were obtained analogous to those of Examples I-III, (V2) - (V-4), VI-2, VII-IX, XIV XIII-1, XIV-2, XV-1, XV -2 and XVI-3, using the following reaction products, containing phosphorus:

   ethoxylated alkyl and aryl acid phosphates, where the alkyl and aryl groups are represented by the methyl, ethyl, butyl, pentyl, hexyl, ootyl, dodecyl, phenyl, tolyl, ohlorophenyl and ootylphenyl groups, propoxylated butylphosphonic acid , propoxylated hydroxymethylphosphonic acid, ethoxylated, propoxylated and chloropropoxylated mono and di-alooyl and aryl-pyrophosphoric acids, where the alkyl and aryl groups are represented by the methyl, ethyl, isopropyl, butyl, octyl,

       chlor-ethyl and tolyl, the products: of phosphorus pentoxide with glycols, such as, for example, ethylene, di-ethylene, triethylene, propylene, dipropylene, neopentyl, octylene, hydroquinone, biphenol, polypropylenes, polyethylenes, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, 1,5-pentanediol, having subsequently reacted with ethylene oxide, of propylene oxide and epichlorohydrin, reaction products of phosphorus pentoxide with a mixture of the above glycols and hydroxy compounds, such as for example water and alcohols, such as for example 2-chloroethyl, butyl , ootyl, allyl and dod-

 <Desc / Clms Page number 25>

 cyle,

   subsequently reacted with ethylene oxide. propylene oxide and epichlorohydrin, the alooxylated products of the reaction of a polyhydroxy compound with phosphorus pentoxide, the polyhydroxy compound being 1,2,6-hexanetriol, glyoerol and pentaerythritol, and so-called "block" polymers: obtained by reacting one or other of the alkoxylated products above with phosphorus pentoxide and by subsequent alkoxylation with ethylene oxide, propylene oxide and epichlorohydrin.



   Bied that in the above examples the replacement of all or part of the polyols normally employed for the preparation of polyurethanes with the phosphorus-containing polyol according to the present invention has been described, it is understood that this covers There are also other methods of incorporating the phosphorus-containing polyol into polyurethanes, so long as they do not depart from the spirit and scope of the present invention.

   By this is meant, for example, processes in which the phosphorus-containing compounds according to the present invention can be reacted with other products, such as for example adipic acid and / or phthalic anhydride as well as others. Polybasic alides and / or anhydrides, to form mixed polyester-based phosphorus polyols, the molecule of which contains at least two active hydrogen atoms, which can subsequently react with polyisocyanates, to form polyurethanes.


    

Claims (1)

CLAIMS 1.- A process for forming a polyurethane having flame-retardant properties, characterized in that a polysccyanate is reacted with a mixture of a polyol and an organic phosphorus compound, the molecule of which contains at least two active hydrogen atoms, and in that the reaction product formed is then cooked. 2. A process according to claim 1, characterized in that the reaction product of the polyisocyanate and the mixture of the polyol and the organic phosphorus compound, the molecule of which contains at least two active hydrogen atoms, is transformed into foam, and in which is then cooked the foam product to form a cellular polyurethane. 3.- Process according to claims 1 and 2, characterized in that the amount of the organic phosphorus compound is 5 to 70% of the total polyol, necessary to react with the polyiocyanate, these percentages being calculated on the active hydrogen equivalents. . 4. A method according to claims 1 and 2, characterized in that the organic phosphorus compound contains more than two active hydrogen atoms per molecule and in that the amount of the organic phosphorus compound is between 30 and 100% of total polyol, necessary to react with the polyisooyanate, these percentages being calculated on the active hydrogen equivalents. 5. A process according to claims 1 to 3, characterized in that the organic phosphorus compound is the reaction product of an alkylene oxide and of a phosphorus acid, the molecule of which contains at least two hydroxyl groups. 6. - Process according to claim 4, characterized in that the organic phosphorus compound is the reaction product of an alkylene oxide and of a phosphorus acid, the molecule of which contains more than two hydroxyl groups, 7. A method according to claims 4 and 6, characterized in that the phosphorus acid is phosphoric acid. 8. - Process according to claim 5, characterized in that the phosphorus acid is a dialkyl-pyrophosphoric acid. <Desc / Clms Page number 27> 9.- Method according to claims 5 and 8, characterized in that EMI27.1 the acid is dibutyl-pyrophoephoric acid. 10. A process according to claims 5 to 9, characterized in that the alkylene oxide is propylene oxide. 11.- Product obtained according to the processes of claims 1 to 10 inclusive.