(19) TZZ ¥_T

(11) EP 2 957 583 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.: 23.12.2015 Bulletin 2015/52 C08G 18/48 (2006.01) C08J 11/10 (2006.01) C08J 11/12 (2006.01) C08G 65/34 (2006.01) (2006.01) (21) Application number: 14460111.9 C08G 18/36

(22) Date of filing: 16.12.2014

(84) Designated Contracting States: (72) Inventors: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • Haponiuk, Józef T. GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO 80-344 Gdansk (PL) PL PT RO RS SE SI SK SM TR • Piszczyk, Lukasz Designated Extension States: 80-107 Gdansk (PL) BA ME • Danowska, Magdalena 80-266 Gdansk (PL) (30) Priority: 18.06.2014 PL 40861014 • Strankowsku, Michal 80-177 Gdansk (PL) (71) Applicant: Novapur Sp. z o.o. 80-233 Gdansk (PL)

(54) Method of obtaining environment-friendly from waste left after of plant oils, and method of obtaining rigid foams

(57) Method of obtaining environment-friendly poly- phuric acid pH 4.5 to 9, preferably from 6.5 to 7.5. Next, ols from waste left after transesterification of plant oils is the reaction mixture is heated under reduced pressure characterized in that the said waste is heated to a tem- to a temperature between 100 and 120°C until water perature in the range between 160 and 240°C, preferably stops to appear. Polyols are also produced from polyg- between 175 and 185°C, under reduced pressure in or- lycols extended with fatty acids and modified fatty acids. der to distill the volatile fraction. The distillation proc eeds The object of the invention is also the method of ob- until no more condensate appears, and the resultant taining polyurethane foams by using polyols that had product has a hydroxyl number between 400 and 1200 been obtained by the method according to the invention. mg KOH/g. Then the mixture is cooled below 100°C, and The foams additionally contain substances which retard acidified with a protonic acid, more preferably with sul- their flammability. EP 2 957 583 A1

Printed by Jouve, 75001 PARIS (FR) 1 EP 2 957 583 A1 2

Description not be completely dehydrated and removed. Moreover, these salts may act as catalysts therefore waste [0001] The object of the invention is the method of ob- is much cheaper than pure glycerol. taining ecological polyols from natural raw materials and [0006] It is well known that dehydration of glycerin at waste as well as the method of obtaining environment- 5 a temperature above 250°C results in obtaining polyg- friendly rigid polyurethane foams with reduced flamma- lycerins with molecular weights between 1 000 and 30 bility that are based on those polyols to be used in con- 000 which are solid at room temperature. Polyglycerins struction and automotive industries. can be used in the production of however [0002] Polyurethanes are polymers consisting of rigid they do not mix with due to high viscosity, and flexible segments. The flexible segments originate 10 hydrophilicity and the large number of hydroxyl groups from hydroxyl-terminated oligomers among which oligo- per molecule. oxypropylenols are the most important compounds ob- [0007] Method of obtaining environment-friendly poly- tained via polymerization of propylene oxide with polyols ols from waste left after transesterification of plant oils is in the presence of KOH as a catalyst. In order to produce characterized, according to the invention, in that the polyurethanes, oligomerols containing from 2 to 8 hy- 15 aforementioned waste is heated to a temperature be- droxyl groups per molecule are used; their molecular tween 160 and 240°C, more preferably under reduced weights range from 600 to 10 000 (Wirpsza, Poliuretany pressure in the temperature range from 175 to 185°C, in - chemia, technologia i stosowanie, 1990). order to distill the volatile phase. The distillation proceeds [0003] In recent years, the increased interest of indus- until no more condensate appears, and the resultant try in polyols from renewable resources has been noted, 20 product has a hydroxyl number between 400 and 1200 polyols being one of the two basic components used in mg KOH/g. Next, the product is cooled down below the synthesis of polyurethane materials. Those renewa- 100°C, acidified with protonic acid, more preferably with ble polyols are "Natural Oil Polyols" (NOPs) which are sulphuric acid pH 4.5 to 9, preferably from 6.5 to 7.5. esters of glycerol and higher unsaturated fatty acids. The Then the reaction mixture is heated under reduced pres- most commonly used oils in polyols production are a) 25 sure to a temperature between 100 and 120°C until water rapeseed oil and sunflower oil In Europe, b) plam oil and stops to appear. coconut oil in Asia, and c) soybean oil in the USA. A [0008] Method of obtaining environment-friendly rigid worldwide interest in obtaining polyols from renewable polyurethane foam In the reaction of premix with raw materials is a result of ever increasing prices of gas agent is characterized according to the inven- and oil. In Poland, rapeseed oil is most commonly used 30 tion by the use of polyol premix which contains environ- for producing polyols. Rapeseed oil is a of ment-friendly polyol produced from waste left after trans- unsaturated higher fatty acids which contains, on aver- esterification of plant oils. The waste is heated to a tem- age, 61% of acid radicals of oleic acid, 21% of acid rad- perature ranging from 160 to 240°C, more preferably icals of linoleic acid, 10% of linolenic radicals and 8% of from 175 to 185°C under reduced pressure, in order to acid radicals originating from higher saturated fatty acids. 35 distill the volatile phase. The distillation proceeds until no The derivatives of rapeseed oil can be used as reactive more condensate appears, and the resultant product has components in the production of polyesters, polyamides a hydroxyl number between 400 and 1200 mg KOH/g. and polyurethanes. Next, the product is cooled down below 100°C, acidified [0004] Methods of obtaining plant polyols are known. with protonic acid, more preferably with sulphuric acid One of the methods is a two-step procedure. In the first 40 pH 4.5 to 9, preferably from 6.5 to 7.5. Then the reaction step, unsaturated fatty acids are subjected to oxidation mixture is heated under reduced pressure to a temper- in order to obtain epoxy derivatives followed by the ring- ature between 100 and 120°C until water stops to appear. opening of in reaction with donors A known isocyanate agent is added in the amount cor- which leads to the creation of hydroxyl groups. Epoxida- responding to the value of IC index between 0.5 to 4.0. tion of plant oils can also be conducted in situ by using 45 [0009] Preferably the flame retardants are added in the acetic acid and hydrogen peroxide or other oxidizing amount ranging from 0.01 to 40 parts by weight of the agents. By modifying plant oils, polyols with hydroxyl foam mass. numbers ranging from couple tens to over 400 mg KOH/g [0010] Preferably phyllosilicate nanofillers are used as and viscosity of couple hundred to over 10 000 mPas flammability-reducing compounds, preferably nanosili- can be obtained. 50 cates, bentonites, smectites, halosites, montmorillonites [0005] In the process of converting plant oils to mo- and/or their modified forms, preferably organophilic mod- noesters of fatty acids, a waste (glycerol phase) is pro- ified with cations of organic salts and/or acid-activated duced which consists of glycerol, water, salts of fatty ac- and/or substituted with transition-metal ions. ids, inorganic salts, an excess of base used to neutralize [0011] Preferably silsesquioxanes are used as nano- the reaction mixture, and remnants of methanol or etha- 55 fillers. nol from transesterification of oils. Glycerol present in the [0012] Preferably the following halogen-free flame re- waste from production is difficult to remove tardants are applied: compounds based on phosphate mainly due to the presence of hydrophilic salts that can- esters, ammonium polyphosphate, phosphites, organo-

2 3 EP 2 957 583 A1 4 phosphates, metal phosphates, red phosphorus, phos- tween 0.5 and 4.0. phorus-basedderivatives of melaminesuch as melamine [0016] Preferably flame retardants are added in the phosphate, melamine pyrophosphate, and other prod- amount ranging from 0.01 to 40 parts by weight relative ucts containing nitrogen and phosphorus derivatives, bo- to the foam mass. ron compounds, preferably zinc borate, melamine bo- 5 [0017] Preferably phyllosilicate nanofillers are used as rates and other boric acid-based derivatives, metal hy- flame retardants, preferably nanosilicates, bentonites, droxides, preferably aluminum hydroxides and magne- smectites, halosites, montmorillonites and/or their mod- sium hydroxides, mineral fillers and additives such as ified forms, preferably organophilic modified with cations ammonium salts, molybdenum derivatives and magne- of organic salts and/or acid-activated and/or substituted sium heptahydrate sulfate, melamine and its derivatives, 10 with transition-metal ions. and expanded graphite. [0018] Preferably silsesquioxanes are used as nano- [0013] Preferably the nanofiller-antipyrene systems fillers. with 0.01 - 20 wt.% of nanofiller and 1 - 40 wt.% of anti- [0019] Preferably halogen-free compounds are used pyrene are used as flame retardants. as flame retardants, i.e. compounds based on phosphate [0014] Another invention is the method of obtaining en- 15 esters, ammonium polyphosphate, phosphites, organo- vironment-friendly polyols from waste left after transes- phosphates, metal phosphates, red phosphorus, phos- terification of plant oils. The waste is heated to a temper- phorus-basedderivatives of melamine such as melamine ature ranging from 160 to 240°C, more preferably from phosphate, melamine pyrophosphate and other products 175 to 185°C under reduced pressure, in order to distill containing nitrogen and phosphorus derivatives, boron the volatile phase. The distillation proceeds until no more 20 compounds, preferably zinc borate, melamine borates condensate appears, and the resultant product has a hy- and other boric acid-based derivatives, metal hydrox- droxyl number between 400 and 1200 mg KOH/g. Next, ides, preferably aluminum hydroxides and magnesium an excess of fatty acids in the form of methyl esters of hydroxides, mineral fillers and additives such as ammo- fatty acids, and plant oils, e.g. rapeseed oil and/or castor nium salts, molybdenum derivatives and magnesium oil and/or tall oil and/or the products of tall oil distillation 25 heptahydrate sulfate, melamine and its derivatives, and and/or linseed oil are added. The mixture is mixed at a expanded graphite. temperature ranging from 160 to 200°C, preferably from [0020] Preferably the nanofiller-antipyrene systems 175 to 185°C, until reaching the constant hydroxyl with 0.01 - 20 wt.% of nanofiller and 1-40 wt.% of anti- number. Then the mixture is cooled below 100°, and acid- pyrene are used as flame retardants. ified with a protonic acid, more preferably with sulphuric 30 [0021] Another invention is the method of obtaining en- acid pH 4.5 to 9, preferably from 6.5 to 7.5. Next, the vironment-friendly polyols from waste left after transes- reaction mixture is heated under reduced pressure to a terification of plant oils. The method is characterized, ac- temperature between 100 and 120°C until water stops cording to the invention, in that the waste is heated to a to appear. temperature in the range between 160 and 240°C. pref- [0015] Method of obtaining environment-friendly rigid 35 erably between 175 and 185°C, under reduced pressure polyurethane foam in the reaction of polyol premix with in order to distill the volatile fraction. The distillation pro- isocyanate agent is characterized, according to the in- ceeds until no more condensate appears, and the result- vention, by the use of polyol premix containing environ- ant product has a hydroxyl number between 400 and ment-friendly polyol obtained from waste left after trans- 1200 mg KOH/g. Next, an excess of fatty acids in the esterification of plant oils. The waste is heated to a tem- 40 form of methyl esters of fatty acids, and plant oils, i.e. perature in the range between 160 and 240°C, preferably rapeseed oil and/or and/or tall oil and/or the between 175 and 185°C, under reduced pressure in or- products of tall oil distillation and/or linseed oil modified der to distill the volatile fraction. The distillation proc eeds with phosphorus- and/or nitrogen-containing moieties until no more condensate appears, and the resultant that retard flammability are added. The mixture is mixed product has a hydroxyl number between 400 and 1200 45 at a temperature ranging from 160 to 200°C. preferably mg KOH/g. Next, an excess of fatty acids in the form of from 175 to 185°C, until reaching the constant hydroxyl methyl esters of fatty acids, and plant oils, i.e. rapeseed number. Then the mixture is cooled below 100°C, and oil and/or castor oil and/or tall oil and/or the products of acidified with a protonic acid, more preferably with sul- talloil distillation and/orlinseed oil areadded. The mixture phuric acid pH 4.5 to 9, preferably from 6.5 to 7.5. Next, is mixed at a temperature ranging from 160 to 200°C, 50 the reaction mixture is heated under reduced pressure preferably from 175 to 185°C, until reaching the constant to a temperature between 100 and 120°C until water hydroxyl number. Then the mixture is cooled below stops to appear. 100°C, and acidified with a protonic acid, more preferably [0022] Method of obtaining environment-friendly rigid with sulphuric acid pH 4.5 to 9, preferably from 6.5 to 7.5, polyurethane foam in the reaction of polyol premix and Next, the reaction mixture is heated under reduced pres- 55 isocyanate agent is characterized, according to the in- sure to a temperature between 100 and 120°C until water vention, in that the applied polyol premix contains envi- stops to appear. A known Isocyanate agent is added in ronment-friendly polyol obtained from waste left after the amount corresponding to the value of IC index be- transesterification of plant oils. The waste is heated to a

3 5 EP 2 957 583 A1 6 temperature in the range between 160 and 240°C, pref- nomena occur. Flames generated during the combustion erably between 175 and 185°C, under reduced pressure of polymers are as dangerous as those associated with in order to distill the volatile fraction. The distillation pro- the burning of other flammable products, e.g. fuels. The ceeds until no more condensate appears, and the result- burning process can be dominated by a radical mecha- ant product has a hydroxyl number between 400 and 5 nism if the accumulation of free radicals or other active 1200 mg KOH/g. Next, an excess of fatty acids in the particles plays a decisive role. The combustion of a pol- form of methyl esters of fatty acids, and plant oils, i.e. ymer depends on the composition, structure, volume, rapeseed oil and/or castor oil and/or tall oil and/or the shape, density, surface porosity, cross-linking density products of tall oil distillation and/or linseed oil modified and other properties of this polymer. Non-modified poly- with phosphorus- and/or nitrogen-containing moieties 10 urethanes are highly flammable. In the case of poly- that retard flammability are added. The mixture is mixed urethane foams, the burning process depends, to a large at a temperature ranging from 160 to 200°C, preferably extent, on their cell structure. Closed-cell polyurethane from 175 to 185°C, until reaching the constant hydroxyl foam burns less easily than open-cell foam because the number. Then the mixture is cooled below 100°C, and latter allows for a so-called stack (chimney) effect. Poly- acidified with a protonic acid, more preferably with sul- 15 urethane decomposition starts at the temperature range phuric acid pH 4.5 to 9, preferably from 6.5 to 7.5. Next, 80-200°C due to the breaking of hydrogen bonds be- the reaction mixture is heated under reduced pressure tween oxygen atoms and NH groups in urethane groups. to a temperature between 100 and 120°C until water In the case of polyurethane obtained from 2,4- toluene stops to appear. A known isocyanate agent is added in diisocyanate (TDI), the breaking of urethane bonds at the amount corresponding to the value of IC Index be- 20 temperatures above 200°C is accompanied by the re- tween 0.5 and 4.0. lease of hydrogen cyanide. Besides, the compounds [0023] Preferably flame retardants are added in the such as, acetonitrile, acrylonitrile, propionitrile, benzoni- amount ranging from 0.01 to 40 parts by weight relative trile, aniline, pyridine and others are also produced. On to the foam mass. the other hand, the main volatile products of the pyrolysis [0024] Preferably phyllosilicate n anofillers are used as 25 of polyurethane obtained from MDI are phenyl Isocy- flame retardants, preferably nanosilicates, bentonites, anates and p-tolueneisocyanates as well as o-benzod- smectites, halosites, montmorillonites and/or their mod- initrile, isoquinoline, and carbohydrogens, e.g. benzene, ified forms, preferably organophilic modified with cations toluene, xylene, biphenyl, naphthalene, carbazole and of organic salts and/or acid-activated and/or substituted others. Benzonitrile dominates among the non-volatile with transition-metal ions. 30 products of decomposition; it undergoes further degra- [0025] Preferably silsesquioxanes are used as nano- dation to hydrogen cyanide. fillers. [0030] A number of methods for reducing the flamma- [0026] Preferably halogen-free compounds are used bility of polyurethane foams is known, as follows: addition as flame retardants, i.e. compounds based on phosphate of flame retardants which do not form chemical bonds esters, ammonium polyphosphate, phosphites, organo- 35 with a polymer (additive agents); addition of flame retard- phosphates, metal phosphates, red phosphorus, phos- ants which react with the foam components (reactive phorus-basedderivatives of melaminesuch as melamine agents); formation of heat-resistant chemical bonds dur- phosphate, melamine pyrophosphate and other products ing the foaming process; usage of flame-retardant aro- containing nitrogen and phosphorus derivatives, boron matic polyisocyanates in the foam production; a combi- compounds, preferably zinc borate, melamine borates 40 nation of the aforementioned methods; and increasing and other boric acid-based derivatives, metal hydrox- the relative content of aromatic rings and polymer cross- ides, preferably aluminum hydroxides and magnesium linking density. The addition of flame retardants, so- hydroxides, mineral fillers and additives such as ammo- called antipyrenes, is the most commonly used method. nium salts, molybdenum derivatives and magnesium These compounds should fulfill the following require- heptahydrate sulfate, melamine and its derivatives, and 45 ments: reduce the overall flammability; reduce the re- expanded graphite. lease of smoke; do not increase the toxicity of gaseous [0027] Preferably the nanofiller-antipyrene systems products of combustion; in the least possible way influ- with 0.01 - 20 wt.% of nanofiller and 1-40 wt.% of anti- ence the performance characteristics of foams; and re- pyrene are used as flame retardants. main in the polyurethane foam during its long-term use. [0028] The advantage of polyols obtained from waste 50 [0031] The impact of antipyrenes on the combustion glycerol and fatty acids is their competitive price com- of polymeric materials has a very complex character. It pared to oligomerols. Moreover, the intro- is based on a couple of concurrent mechanisms among duction of chemical moieties that retard flammability al- which one is generally dominant, however, as time lows for producing polyurethane foams which are char- progresses, another mechanism can take over. This acterized by increased fire resistance. 55 makes it difficult to precisely determine the mechanism [0029] As is the case with other man-made materials, of action of flame retardant. The complexity of this phe- the mechanism of polyurethane combustion is a complex nomenon depends on many factors, inter alia, chemical process in which numerous physical and chemical phe- composition of polymer and antipyrene, and physical

4 7 EP 2 957 583 A1 8 properties of the final product. ers. [0032] Halogen-free flame retardants are a group of [0037] Rigid polyurethane foams modified with both flame retarding agents used in the synthesis of poly- compounds displayed better flame resistance compared urethane foams. Expanded graphite and phosphorus- to the foams filled with just one flame retardant. and nitrogen-containing compounds are the most com- 5 [0038] The use of polyols obtained from plant oils monly used substances of this type. (rapeseed, soybean, sunflower and linseed oils) for mod- [0033] The mechanism of action of phosphorus-con- ifying the composition of polyurethane systems of petro- taining antipyrene depends on the type and structure of chemical origin was described in the published paper flame retardant and the polymer matrix. During the com- (Prociak A.: Polimery 2008, 53, no. 3, p.195-200). The bustion of polymers, phosphorus-containing antipyrenes 10 introduction of polyols from vegetable oils into the polyol act in the condensed or gas phase as well as in both mix used in the production of rigid polyurethane foams these phases at the same time. In the condensed phase, allows for obtaining porous materials with good thermoin- antipyrenes influence the mechanism and rate of thermal sulating characteristics that surpass those of the prod- decomposition of polymer, while in the gas phase they ucts made exclusively from petrochemical polyols. The act as sweeper molecules against free radicals. Thermal 15 addition of more than 30 wt.% of plant polyols to the polyol decomposition of phosphorus compounds in the con- premix can negatively affect the foaming process in the densed phase is accompanied by the formation of phos- reaction mix due to the opening of pores. This results in phoric acid and polyphosphoric acid. Both these acids the increased value of thermal conductivity coefficient of form a high-viscosity thin layer on the surface of burnt the final product. polymer, which protects it against oxygen and heat.20 [0039] In the published study (Pielichowski J. et al.: Phosphorus is a catalyst in the reaction of carbonization Polimery 2005, 50, no. 10, p.723-727) the authors used which takes place during polymer combustion. Thin coat- glycerol as a ring-opening factor to open the oxirane rings ings of glassy material may form on the surface of the in epoxidized plant oils in order to obtain polyol raw ma- layers which becomes an additional obstacle for mass terials for the polyurethane foams systems. Soybean and heat transfer between the solid and gas phases in 25 polyols used together with glycerol have the desired vis- the burning material. cosity, and they form homogenous premixes with other [0034] Nitrogen-containing flame retardants act simi- typical polyols used in the production of rigid poly- larly to their phosphorus-containing counterparts. The urethane foams. The foams made from a polyol mix con- most commonly used nitrogen-containing flame retard- sisting of 50 wt.% of soybean polyol are characterized 30 ants are melamine (C 3N3(NH2)) and urea (NH 2CONH2). by good performance characteristics. Burning nitrogen compounds absorb heat. They release [0040] In the published study (Harikrishnan G.: Ind. gaseous nitrogen, which dilutes toxic gases originating Eng. Chem. Res., 45, 2006 p. 7126-7134) rigid poly- from the matrix decomposition, and form a charcoal layer urethane foams were modified with natural montmorillo- on the polymer surface. The latter limits heat transfer to nite (MMT). The authors evaluated the effect of nanofiller the polymerand the releaseof flammableand toxic gases 35 on the performance characteristics of products. in com- from the material. As a consequence, the flammability of parison to non-modified foams, the nanofiller-containing the material is reduced. foams had better performance characteristics. [0035] Nanofillers are a relatively new group of mate- [0041] A method of obtaining self-extinguishing rigid rials introduced into the polymer matrix as flame retard- polyurethane foam has been described in the Polish pat- ants. These compounds improve thermal stability and 40 ent Pat 189670 as follows: 1-4 parts by weight of sur- mechanical properties as well as increase the barrier ca- factant, 50-100 parts of polyol (Rokopol RF 551), 2-60 pacity. Mainly due to improved thermal stability and in- parts of mono- or diphosphate of tri(diethanolaminome- creased barrier capacity, nanofillers were considered to thyl)melamine, alternatively up to 40 parts of aliphatic be used in polymeric materials for improving their flame bromo derivatives, 5-50 parts of porophor, and 0.1-7 resistance. The most common nanofillers used as flame 45 parts of catalyst (dibutyltin dilaurate) were mixed togeth- retardants in polymers are phyllosilicates. In the pub- er. From 7 to 90 parts by weight of polymeric 4,4’-diphe- lished study (Czupryn´ski B.; Polimery 2008,53,no. 2, p. nylmethane diisocyanate were added to the polyol 133-137) rigid polyurethane foams were modified with premix. Next, the reaction mixture was mixed and poured powder fillers (aluminum hydroxide, melamine, starch, into a mold. According to the above invention, it has been talcum, chalk and borax). The authors evaluated the ef- 50 stated that the use of antipyrenes of Polish origin did not fect of each filler on the performance characteristics of significantly increase the costs of polyurethane foam pro- the final products, particularly on their flammability char- duction, while the application of dibutyltin dilaurate as a acteristics. catalyst reduced the use of harmful amines in the pro- [0036] In another publication (Modesti M.: Polymer duction process. Degradation and Stability 77, 2002, p. 195-202) the syn- 55 [0042] The invention described in the Polish patent ap- thesis of rigid polyurethane foams with fillers such as, plication P.339246 relates to the environment-friendly expanded graphite and triethyl phosphate was de- rigid polyurethane foam with reduced flammability. The scribed, including the synergistic effect of combined fill- used polyol premix contained 34-79 parts by weight of

5 9 EP 2 957 583 A1 10 dibromobutenediol, 5-35 parts of 2-(2-hydrox-[0046] According to the invention, halogen-free (main- yethoxy)ethyl-2-hydroxypropyl-3,4,5,6-tetrabromoph- ly phosphorus- and nitrogen-containing compounds), na- thalate, 10-20 parts of porophor composed of pentane nofillers and the flame-retarding systems consisting of and water mix, 5-30 parts of additive antipyrene tri(2- nanofiller and halogen-free antipyrene were applied as chloropropyl) phosphate, alternatively N,N-dimethylcy- 5 flame retardants. clohexylamine as a catalyst, and surfactant, i.e. organo- [0047] According to the invention, in order to obtain silicate-polyester copolymer with isocyanate agent. Ac- environment-friendly rigid polyurethane foams with re- cording to the above description, it was demonstrated duced flammability, appropriate amounts of polyetherols, that the use of two reactive antipyrenes, i.e. one with mixture of catalysts, surfactant, environment-friendly bromine bonded to carbon in an aliphatic compound or 10 foaming agent in the form of pentane fraction and water, to carbon in an aromatic compound, and the other being and isocyanate agent are mixed to the effect that the additive antipyrene results in the synergistic effect of the value of IC index ranges from 0.5 to 4.0. two antipyrenes. The oxygen index of such foams ranges [0048] Preferablycatalysts such as,potassium acetate from 24.0 to 27.6. However, it should be pointed out that solution, sodium acetate in , solution of numerous studies are presently conducted to develop 15 sodium acetate in diethylene glycol, 1,3,5-tris(3-dimeth- flame retarded polymers that do not contain halogenated ylaminopropyl)hexahydro-s-triazine, 2-[2(dimethylami- additives, including the brominated ones. no)ethoxy]ethanol, tin 2-ethylhexanoate, dibutyltin lau- [0043] The invention described in the Polish patent rate and Dabco-like catalysts, e.g. Dabco 33 LV (solution Pat198605 relates to the environment-friendly rigid poly- of 1,4-diazabicyclo[2.2.2]octane in ethylene glycol) or urethane foam with reduced flammability. The foam is 20 their mixtures. the reaction product of the following components: 24-90 [0049] Preferably the compounds such as, polyglycer- parts by weight of polyol premix, 1.0-2.5 parts relative to ols and polyglycerols extended with methyl esters of fatty polyol premix of foaming catalyst, 1.5-4.0 parts of sur- acids, rapeseed oil, castor oil, tall oil and the products of factant, 10-30 parts of foaming agent, bromine- and Its distillation, and linseed oil are used as environment- phosphorus-containing antipyrenes In the amount from 25 friendly polyol components. 5 to 40 wt.% relative to premix mass and isocyanate [0050] In order to reduce flammability, it is preferable agent. The reaction mixture contains trimerization cata- to use the environment-friendly component of polyol mix- lyst in the amount of 3.0-5.0 parts by weight relative to ture that contains flame-retarding moieties, nanofillers the calculated excess of isocyanate agent. According to and/or halogen-free flame retardants and/or the flame- the above invention, it was stated that by using a system 30 retarding systems consisting of nanofiller and halogen- consisting of two antipyrenes, an excess of isocyanate free flame retardant. agent, and trimerization catalyst, rigid polyurethane [0051] The advantage of obtaining the new, environ- foams with the oxygen index higher than that of non- ment-friendly rigid polyurethane foam is the use of envi- modified foams can be obtained. At present, the EU reg- ronment-friendly polyol in the amount ranging from 1 to ulations oblige manufacturers to produce halogen-free 35 100 parts by weight. Because of the presence of reactive compositions. hydroxyl groups -OH, the environment-friendly polyol [0044] Method of obtaining environment-friendly poly- component is built into the polymer structure, which im- urethane foam according to the invention is based on the proves its mechanical properties. The presence of envi- use of environment-friendly component of polyol mix ronment-friendly polyol component in the produced rigid such as, polyglycerol, polyglycerol extended with fatty 40 polyurethane foams significantly improves physico-me- acids (e.g. methyl esters of fatty acids, rapeseed oil, cas- chanical properties of the material and slows down its tor oil, tall oil and the products of its distillation, and lin- burning. seed oil) and polyglycerol extended with modified fatty [0052] The main advantage of new, environment- acids. The application of the aforementioned polyol com- friendly rigid polyurethane foam with reduced flammabil- ponent positively affects the performance characteristics 45 ity is the use of environment-friendly polyol component of the obtained polyurethane foams as well as reduces which contains flame-retarding moieties, halogen-free the production costs. retardants, and nanofillers in the amount ranging from [0045] Method of obtaining environment-friendly poly- 0.01 do 40.00 parts by weight. The use of nanofillers In urethane foams with reduced flammability according to the production of rigid polyurethane foams significantly the invention relates to obtaining new oligomerols in the 50 improves mechanical properties and the barrier capacity first step, which include the following: environment- of the final products. Preferably the systems consisting friendly polyol component or environment-friendly polyol of nanofiller and halogen-free retardant should be used. component containing flame-retarding moieties, halo- [0053] The invention is described further in the follow- gen-free flame retardant, nanofiller or the systems com- ing examples of method implementation. posed of nanofiller and halogen-free flame retardant.55 Then the new oligomerols should be used to obtain en- Example 1 vironment-friendly polyurethane foams with reduced flammabilityand improved mechano-physical properties. [0054] 340 g of alkaline raw glycerol effluent, originat-

6 11 EP 2 957 583 A1 12 ing from methanolysis of rapeseed oil, is slowly heated 3 g of 85% aqueous solution of phosphoric acid H3PO4 up to 180°C under reduced pressure in the reactor and 150 g of biodiesel are added to the obtained envi- equipped with a distillation column in order to remove ronment-friendly polyol, and the mixture is heated to methanol and water. The process is terminated when the 100°C. After 1 hour, the mixture is heated to 160°C under condensation of distillate stops. The obtained 5 oli- reduced pressure for 5 hrs. The obtained oligoetherol is goetherol (environment-friendly polyol) is characterized characterized by a hydroxyl number in the range from by a hydroxyl number in the range 550-650 mg KOH/g 250 to 350 mg KOH/g and brown color. and brown color. Next, the obtained oligomerol is cooled down to 60°C, and the appropriate amounts of 50% so- Example 5 lution of sulfuric acid and toluene are added under stir- 10 ring. The obtained product is centrifuged at 3500 rpm for [0058] Rigid polyurethane foam was prepared as fol- 10 min. The mixture separates into two parts (sediment lows: 30 parts by weight of the reaction product after the and polyglycerol fraction). Polyglycerol fraction is trans- reaction between oxypropylene and sorbitol (Rokopol RF ferred into the reactor and heated to a temperature of 551) and 70 parts by weight of environment-friendly poly- 15 110°C in order to remove toluene. The obtained oli- ol with LOH 550 - 650 mg KOH/g were combined. Next, goetherol is characterized by a hydroxyl number between 1.5 parts by weight of 33% solution of potassium acetate 550 and 650 mg KOH/g and brown color. in ethylene glycol as a catalyst, 1.5 parts of 1,3,5-tris(3- dimethylaminopropyl)hexahydro-s-triazine catalyst, in- Example 2 terchangeable with 2-[2(dimethylamino)-ethoxy]ethanol, 20 and 4 parts of surfactant (SC-246 silicone oil) were added [0055] Rigid polyurethane foam was produced as fol- and thoroughly mixed. Then 2 parts by weight of n-pen- lows: 30 parts by weight of the reaction product after the tane (foaming agent) and 4 parts by weight of water rel- reaction between oxypropylene and sorbitol (Rokopol RF ative to polyol premix were added. The flame retardant 551) and 70 parts by weight of environment-friendly poly- system consisting of expanded graphite and montmo- ol obtained as described in Example 1 (oligoetherol with 25 rillonite modified with quaternary ammonium salt in the LOH 550 - 650 mg KOH/g) were combined. Next, 1.5 parts amount of 15 parts by weight relative to polyol mixture by weight of 33% solution of potassium acetate in ethyl- was used. The relative use of both system components ene glycol as a catalyst, 1.5 parts of 1,3,5-tris(3-dimeth- was 5 parts by weight of modified montmorillonite and ylaminopropyl)hexahydro-s-triazine catalyst, alterna- 10 parts of expanded graphite. Such prepared premix tively with 2-[2(dimethylamino)-ethoxy]ethanol, and 4 30 was completely homogenized and then 80 parts by parts of surfactant (SC-246 silicone oil) were added. The weight of isocyanate agent (pMDI) were mixed into it for mixture was thoroughly mixed and then 2 parts by weight 10 sec. of n-pentane (foaming agent) and water (4 parts by weight relative to polyol premix) were added. After com- Example 6 plete homogenization of this premix, 80 parts by weight 35 of polymeric isocyanate agent (4,4’-diisocyanatetoluene, [0059] Rigid polyurethane foam was prepared as fol- pMDI) were mixed into it for 10 sec. lows: 30 parts by weight of the reaction product after the reaction between oxypropylene and sorbitol (Rokopol Example 3 D1002) and 35 parts by weight of environment-friendly 40 polyol with LOH = 250-350 mg KOH/g were combined. [0056] Rigid polyurethane foam was obtained as in Ex- Next, 1.5 parts by weight of 1,3,5-tris(3-dimethylamino- ample 2 however the reaction mixture had been modified propyl)hexahydro-s-triazine catalyst, 1 part of by the use of nanofillers. Montmorillonite modified with 2-[2-(dimethylamino)ethoxy]ethanol catalyst, and 4 parts quaternary ammonium salt in the amount of 10 parts by of surfactant (SC-246 silicone oil) were added and thor- weight was used as a modifier. Such prepared premix 45 oughlymixed. Then 2 parts by weight of n-pentane (foam- was completely homogenized and later mixed with 80 ing agent) and 4 parts by weight of water relative to polyol parts by weight of isocyanate agent (pMDI) for 10 sec. premix were added. The flame retardant system consist- ing of phosphate polyester and montmorillonite modified Example 4 with quaternary ammonium salt in the amount of 10 parts 50 by weight relative to polyol mixture was used. The relative [0057] 1 000 g of alkaline raw glycerol effluent, origi- use of both system components was 5 parts by weight nating from methanolysis of rapeseed oil, is slowly heat- of modified montmorillonite and 5 parts of phosphate pol- ed up to 180°C under reduced pressure and stirring in yester relative to polyol premix. Such prepared premix the reactor equipped with a distillation column in order was completely homogenized and then 80 parts by to remove methanol and water. The process is terminat- 55 weight of isocyanate agent (pMDI) were mixed into it for ed when the condensation of distillate stops. The ob- 10 sec. tained oligoetherol is characterized by a hydroxyl number In the range of 550-650 mg KOH/g and brown color. Next,

7 13 EP 2 957 583 A1 14

Example 7. for 10 sec.

[0060] 1 000 g of alkaline raw glycerol effluent, origi- nating from methanolysis of rapeseed oil, is heated up Claims to 180°C under reduced pressure and stirring in the re- 5 actor equipped with a distillation column in order to re- 1. Method of obtaining environment-friendly polyols move methanol and water. The process is terminated from waste left after transesterification of plant oils when the condensation of distillate stops. The obtained characterized in that the waste is heated to a tem- oligoetherol is characterized by a hydroxyl number of 628 perature In the range between 160 and 240°C, pref- mg KOH/g and brown color. Next, 3 g of 85% aqueous 10 erably between 175 and 185°C, under reduced pres- solution of H3PO4 and 150 g of fatty acid with phospho- sure, distillating the volatile fraction until no more rus-containing moieties that retard flammability are add- condensate appears and the resultant product hav- ed to the obtained polyol, and the mixture is heated to ing a hydroxyl number between 400 and 1200 mg 100°C. After 1 hour, the mixture is heated to 160°C under KOH/g is obtained, which is next cooled down below reduced pressure for 5 hrs. The obtained oligoetherol is 15 100°C, then acidified with protonic acid, more pref- characterized by a hydroxyl number in the range from erably with sulphuric acid pH 4.5 to 9, preferably from 150 to 300 mg KOH/g and brown color. 6.5 to 7.5 and next the reaction mixture is heated under reduced pressure to a temperature between Example 8 100 and 120°C until water stops to appear. 20 [0061] Rigid polyurethane foam was prepared as fol- 2. Method of obtaining environment-friendly rigid poly- lows: 30 parts by weight of the reaction product after the urethane foam in the reaction of polyol premix with reaction between oxypropylene and sorbitol (Rokopol RF isocyanate agent characterized in that the applied 551) and 70 parts by weight of environment-friendly poly- polyol premix containing environment-friendly polyol ol with flame-retarding phosphorus-containing moieties 25 obtained from waste left after transesterification of and a hydroxyl number LOH = 150-300 mg KOH/g were plant oils is heated to a temperature in the range combined. Next, 1.5 parts by weight of 33% solution of between 160 and 240°C, preferably between 175 potassium acetate in ethylene glycol as a catalyst, 1.5 and 185°C, under reduced pressure distillating the parts of 1,3,5-tris(3-dimethylaminopropyl)hexahydro-s- volatile fraction, until no more condensate appears triazine catalyst, alternatively with 2-[2-(dimethylami-30 and the resultant product having a hydroxyl number no)ethoxy]ethanol catalyst, and 4 parts of surfactant (SC- between 400 and 1200 mg KOH/g is obtained, which 246 silicone oil) were added and thoroughly mixed. Then is next cooled down below 100°C, acidified with pro- 2 parts by weight of n-pentane (foaming agent) and 4 tonic acid, more preferably with sulphuric acid pH parts by weight of water relative to polyol premix were 4.5 to 9, preferably from 6.5 to 7.5 and next the re- added. Such prepared premix was completely homoge- 35 action mixture is heated under reduced pressure to nized and then 80 parts by weight of isocyanate agent a temperature between 100 and 120°C until water (pMDI) were mixed into it for 10 sec. stops to appear, and a known isocyanate agent Is added in the amount corresponding to the value of Example 9 IC index between 0.5 and 4.0. 40 [0062] Rigid polyurethane foam was prepared as fol- 3. Method according to claim 2 characterized in that lows: 10 parts by weight of the reaction product after the flame retardants are added in the amount ranging reaction between oxypropylene and sorbitol (Rokopol RF from 0.01 to 40 parts by weight relative to the foam 551) and 90 parts by weight of environment-friendly poly- mass. ol with flame-retarding phosphorus-containing moieties 45 and a hydroxyl number LOH = 150-300 mg KOH/g were 4. Method according to claim 3 characterized in that combined. Next, 1.5 parts by weight of 33% solution of phyllosilicate nanofillers are used as flame retard- potassium acetate in ethylene glycol as a catalyst, 1.5 ants, preferably nanosilicates, bentonites, smec- parts of 1,4-diazabicyclo[2.2.2]octane solution in ethyl- tites, halosites, montmorillonites and/or their modi- ene glycol as a catalyst, and 4 parts of surfactant (SC- 50 fied forms, preferably organophilic modified with cat- 246 silicone oil) were added and thoroughly mixed. Then ions of organic salts and/or acid-activated and/or 4 parts by weight of water relative to polyol premix were substituted with transition-metal ions. added. The flame retardant system consisting of phos- phate polyester and montmorillonite modified with qua- 5. Method according to claim 3 characterized in that ternary ammonium salt in the amount of 10 parts by55 silsesquioxanes are used as nanofillers. weight was used as flame retardant. Such prepared premix was completely homogenized and then 80 parts 6. Method according to claim 3 characterized in that by weight of isocyanate agent (pMDI) were mixed into it halogen-free compounds from the group of: com-

8 15 EP 2 957 583 A1 16

pounds based on phosphate esters, ammonium from 160 to 200°C, preferably from 175 to 185°C, polyphosphate, phosphites, organophosphates, until reaching the constant hydroxyl number and next metal phosphates, red phosphorus, phosphorus- cooled below 100°C, and acidified with a protonic based derivatives of melamine such as melamine acid, preferably with sulphuric acid pH 4.5 to 9, pref- phosphate, melamine pyrophosphate and other5 erably from 6.5 to 7.5 and next the reaction mixture products containing nitrogen and phosphorus deriv- is heated under reduced pressure to a temperature atives, boron compounds, preferably zinc borate, between 100 and 120°C until water stops to appear melamine borates and other boric acid-based deriv- and a known isocyanate agent is added in the atives, metal hydroxides, preferably aluminum hy- amount corresponding to the value of IC index be- droxides and magnesium hydroxides, mineral fillers 10 tween 0.5 and 4.0. and additives such as ammonium salts, molybde- num derivatives and magnesium heptahydrate sul- 10. Method according to claim 9 characterized in that fate, melamine and its derivatives, and expanded flame retardants are added in the amount ranging graphite, are used as flame retardants. from 0.01 to 40 parts by weight relative to the foam 15 mass. 7. Method according to claim 3 characterized in that nanofiller-antipyrene systems with 0.01 - 20 wt.% of 11. Method according to claim 10 characterized in that nanofiller and 1-40 wt.% of antipyrene are used as phyllosilicate nanofillers are used as flame retard- flame retardants. ants, preferably nanosilicates, bentonites, smec- 20 tites, halosites, montmorillonites and/or their modi- 8. Method of obtaining environment-friendly polyols fied forms, preferably organophilic modified with cat- from waste left after transesterification of plant oils ions of organic salts and/or acid-activated and/or characterized in that the waste is heated to a tem- substituted with transition-metal ions. perature in the range between 160 and 240°C, pref- erably between 175 and 185°C, under reduced pres- 25 12. Method according to claim 10 characterized in that sure distillating the volatile fraction, until no more silsesquioxanes are used as nanofillers. condensate appears and the resultant product hav- ing a hydroxyl number between 400 and 1200 mg 13. Method according to claim 10 characterized in that KOH/g is obtained, next fatty acids from the group halogen-free compounds from the group of: com- of: methyl esters of fatty acids, and plant oils in the 30 pounds based on phosphate esters, ammonium form of rapeseed oil and/or castor oil and/or tall oil polyphosphate, phosphites, organophosphates, and/or the products of tall oil distillation and/or lin- metal phosphates, red phosphorus, phosphorus- seed oil are added in excess, then the mixture is based derivatives of melamine such as melamine mixed at a temperature ranging from 160 to 200°C. phosphate, melamine pyrophosphate and other preferably from 175 to 185°C, until reaching the con- 35 products containing nitrogen and phosphorus deriv- stant hydroxyl number and next cooled below 100°C, atives, boron compounds, preferably zinc borate, and acidified with a protonic acid, preferably with sul- melamine borates and other boric acid-based deriv- phuric acid pH 4.5 to 9, preferably from 6.5 to 7.5. atives, metal hydroxides, preferably aluminum hy- and next, the reaction mixture is heated under re- droxides and magnesium hydroxides, mineral fillers duced pressure to a temperature between 100 and 40 and additives such as ammonium salts, molybde- 120°C until water stops to appear. num derivatives and magnesium heptahydrate sul- fate, melamine and its derivatives, and expanded 9. Method of obtaining environment-friendly rigid poly- graphite, are used as flame retardants. urethane foam in the reaction of polyol premix with isocyanate agent characterized in that the applied 45 14. Method according to claim 10 characterized in that polyol premix containing environment-friendly polyol nanofiller-antipyrene systems with 0.01 - 20 wt.% of obtained from waste left after transesterification of nanofiller and 1-40 wt.% of antipyrene are used as plant oils is heated to a temperature in the range flame retardants. between 160 and 240°C, preferably between 175 and 185°C, under reduced pressure distillating the 50 15. Method of obtaining environment-friendly polyols volatile fraction until no more condensate appears from waste left after transesterification of plant oils and the resultant product having a hydroxyl number characterized in that the waste is heated to a tem- between 400 and 1200 mg KOH/g is obtained, next perature in the range between 160 and 240°C, pref- fatty acids from the group of methyl esters of fatty erably between 175 and 185°C, under reduced pres- acids, and plant oils in the form of rapeseed oil and/or 55 sure distillating the volatile fraction until no more con- castor oil and/or tall oil and/or the products of tall oil densate appears and the resultant product having a distillation and/or linseed oil are added in excess, hydroxyl number between 400 and 1200 mg KOH/g then the mixture is mixed at a temperature ranging is obtained, next fatty acids from the group of methyl

9 17 EP 2 957 583 A1 18

esters of fatty acids, and plant oils in the form of: silsesquioxanes are used as nanofillers. rapeseed oil and/or castor oil and/or tall oil and/or the products of tall oil distillation and/or linseed oil 20. Method according to claim 17 characterized in that modifed with phosphorus" and/or nitrogen-contain- halogen-free compounds from the group of: com- ing moieties that retard flammability are added in ex- 5 pounds based on phosphate esters, ammonium cess, then the mixture is mixed at a temperature polyphosphate, phosphites, organophosphates, ranging from 160 to 200°C, preferably from 175 to metal phosphates, red phosphorus, phosphorus- 185°C, until reaching the constant hydroxyl number based derivatives of melamine such as melamine and next cooled below 100°C, and acidified with a phosphate, melamine pyrophosphate and other protonic acid, preferably with sulphuric acid pH 4.5 10 products containing nitrogen and phosphorus deriv- to 9, preferably from 6.5 to 7.5 and next the reaction atives, boron compounds, preferably zinc borate, mixture is heated under reduced pressure to a tem- melamine borates and other boric acid-based deriv- perature between 100 and 120°C until water stops atives, metal hydroxides, preferably aluminum hy- to appear. droxides and magnesium hydroxides, mineral fillers 15 and additives such as ammonium salts, molybde- 16. Method of obtaining environment-friendly rigid poly- num derivatives and magnesium heptahydrate sul- urethane foam in the reaction of polyol premix with fate, melamine and its derivatives, and expanded isocyanate agent characterized In that the applied graphite, are used as flame retardants. polyol premix containing environment-friendly polyol obtained from waste left after transesterification of 20 21. Method according to claim 17 characterized in that plant oils is heated to a temperature in the range nanofiller-antipyrene systems with 0.01 - 20 wt.% of between 160 and 240°C, preferably between 175 nanofiller and 1-40 wt.% of antipyrene are used as and 185°C, under reduced pressure distillating the flame retardants. volatile fraction until no more condensate appears and the resultant product having a hydroxyl number 25 between 400 and 1200 mg KOH/g is obtained, next fatty acids from the group of methyl esters of fatty acids, and plant oils in the form of: rapeseed oil and/or castor oil and/or tall oil and/or the products of tall oil distillation and/or linseed oil modified with30 phosphorus- and/or nitrogen-containing moieties that retard flammability are added in excess, then the mixture is mixed at a temperature ranging from 160 to 200°C, preferably from 175 to 185°C, until reaching the constant hydroxyl number and then the 35 mixture is cooled below 100°C, and acidified with a protonic acid, preferably with sulphuric acid pH 4.5 to 9, preferably from 6.5 to 7.5 and next, the reaction mixture is heated under reduced pressure to a tem- perature between 100 and 120°C until water stops 40 to appear and a known isocyanate agent is added in the amount corresponding to the value of IC index between 0.5 and 4.0.

17. Method according to claim 16 characterized in that 45 flame retarding compounds are added in the amount ranging from 0.01 to 40 parts by weight relative to the foam mass.

18. Method according to claim 17 characterized in that 50 phyllosilicate nanofillers are used as flame retard- ants, preferably nanosilicates, bentonites, smec- tites, halosites, montmorillonites and/or their modi- fied forms, preferably organophilic modified with cat- ions of organic salts and/or acid-activated and/or 55 substituted with transition-metal ions.

19. Method according to claim 17 characterized in that

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• PL 189670 [0041] • PL 198605 [0043] • PL P339246 [0042]

Non-patent literature cited in the description

•CZUPRYN´ SKI B. Polimery, 2008, vol. 53 (2), • PIELICHOWSKI J. et al. Polimery, 2005, vol. 50 (10), 133-137 [0035] 723-727 [0039] • MODESTI M. Polymer Degradation and Stability, • HARIKRISHNANG. Ind. Eng. Chem. Res., 2006, vol. 2002, vol. 77, 195-202 [0036] 45, 7126-7134 [0040] • PROCIAK A. Polimery, 2008, vol. 53 (3), 195-200 [0038]

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