CS255342B1 - Method of polyurethans or polyurethan-isocyanurates production - Google Patents

Description

The invention relates to a process for the production of polyurethanes or polyurethane isocyanurates, in particular polyurethane and / or isocyanurate-modified foams of polyester polyols and / or polyether polyols of unusual composition and compounds containing at least one active hydrogen, catalyst and auxiliaries, by reaction with di- to polyisocyanates.

Polyurethanes are generally prepared from two basic components, a polyol component and diisocyanates to polyisocyanates. The composition of the polyol component depends on the processing method and the type of polyurethane being prepared. It generally consists of polyester polyol and / or polyether polyol, a catalyst, a suds stabilizer, an emulsifier, a light stabilizer, a flame retardant, a blowing agent, and optionally other excipients.

The starting polyester polyols and / or polyether polyols used in the chemistry of polyurethanes are usually well-defined compounds based on pure raw materials. From economic and environmental, often technical advantages, polyesterpolyols and polyetherpolyols based on secondary raw materials are used for the preparation of polyurethanes (cf. author's certificates 218170 and 229 429J). These raw materials have a wider range of qualitative indicators and can be used mainly for the production of such polyesterpolyols or For example, polyester polyols or polyether polyols for rigid polyurethane or polyurethane isocyanurate foams from defined raw materials have a hydroxyl number with an accuracy of 20 to 30 mg KOH / g, in particular 450 + 20 mg KOH / g. It is often the case that the prepared polyesterpolyol or polyetherpolyol has unsatisfactory properties, in particular hydroxyl group content.Polyetherpolyols or polyesterpolyols for soft foams, adhesives and varnishes have a low hydroxyl number, e.g. 48 mg KOH / g, usually specified. with an accuracy of + 3 mg KOH / / gram, the use of secondary raw materials for their preparation cannot, for obvious technical reasons, achieve this margin for the products prepared. This is also one of the reasons why polyester polyols and / or polyether polyols are not prepared for low hydroxyl number polyurethanes from secondary raw materials.

According to the present invention, a process for the preparation of a polyol component of polyester polyol and / or polyether polyol, preferably for the production of polyurethanes and polyurethane or polyurethane isocyanurate foams from non-complying hydroxyl number compounds preferably containing the necessary impurities such as activators, stabilizers, emulsifiers, blowing agents, flame retardants The fillers, dyes are carried out in such a way that 0.1 to 15% by weight of the basic polyol, preferably having a hydroxyl value of 30 to 800 mg KQH / g, is added. compounds with at least 1 active hydrogen having a hydroxyl number of 20 to 2000 mg

KOH / g.

The advantage of the process according to the invention is the possibility to utilize a wide range of polyester polyols and polyether polyols made from non-traditional raw materials, including secondary raw materials, and to technically modify the properties of the oxygen components of polyurethanes and polyurethane isocyanurates by technically and economically available polyols. chemical and other utility properties of extruded polyurethanes or polyurethane isocyanurates.

Furthermore, flexible according to the need to change the product range and, last but not least, to exploit the synergism of multi-polyol.

A wide variety of active hydrogen compounds can be used to formulate the hydroxyl group content of the present invention to formulate a polyol component for polyol polyurethanes and excipients. If the hydroxyl group content of the polyol used is low, it is suitable to use a low molecular weight, preferably liquid polyhydric compound with a high content of active hydrogen, expressed as hydroxyl value in mg KOH / g, e.g. methanol, ethylene glycol and other glycols, glycerol, trimethylolpropane, pentaerythritol and the like. Other properties of the polyol, e.g. viscosity. The high hydroxyl number polyol versus the desired polyol is treated with high molecular weight liquid compounds with a low hydroxyl group content, e.g. polyether polyols having a hydroxyl group content of 20 to 100 mg KOH / g, in the case of modification and viscosity of the polyol used, are polyester polyols or mixtures thereof with other compounds.

The described process for the preparation of the polyol or polyol component can advantageously be used in a polyol production plant and, after analysis, the hydroxyl number of the polyol can be adjusted directly in the production plant, optionally with the addition of other necessary additives.

Suitable polyester polyols may be polyester polyols from secondary raw materials or polyester polyols or mixtures thereof with polyester polyols based on dicarboxylic acids and / or their anhydrides with divalent to polyhydric alcohols and / or polyether polyols.

Suitable polyether polyols which can be used for mixtures with a polyether polyol are addition products, in particular polyaddition with a low molecular weight epoxy compound or a mixture of epoxy compounds such as ethylene oxide, propylene oxide, epichlorohydrin with a polyhydric alcohol such as glycerol, polyethylpentol polypropane, polyethyl polypropane. Suitable isocyanate components according to the invention are organic di- to polyisocyanates, e.g. arylpolyisocyanates of ben255342 zene or naphthalene ‘series, which are more reactive and less toxic than aliphatic diisocyanates to polyisocyanates. These are:

2.4- tol ué n diizok y aná t

2,6-toluenediisocyanate and mixtures thereof.

Other diisocyanates may be used, e.g.

phenylenediisocyanate, α-naphthalenediisocyanate,

4-toluene diisocyanate, n-hexylene diisocyanate, methylene bis (4-phenylene diisocyanate) methane,

3,3'-ditoluén-4,4'-diizokyan.át.

4,4 metándifenyldiizokyanát.

3,3'-dimethoxy-4,4'-difenyléndiizokyanát,

1, 5-iiaítaléndiizokyanát,

2.4- chloroEenylene diisocyanate, hexamelylene diisocyanate,

1.3-cyclopentylene diisocyanate,

1,2-cyclohexylenediisocyanate,

1,4-cyclohexylenediisocyanate.

cy klopene tyldiisocyanate t, cyclohexylidene diisocyanate, p-phenylene diisocyanate, m-ethylene diisocyanate.

4,4‘-diphenylpropanediisocyanate, 1-methyl-2,4-phenylenediisocyanate,

4,4 ^: -dii'enyIndiisocyanate,

1.2- propylene diisocyanate,

1,2-butylenediisocyanate, ethylidene diisocyanate, propylidene diisocyanate, butylidene diisocyanate,

3,5-triisocyanobenzene,

2,4 6-triisocyanato-toluene.

2,4,6 triazocyanato-chlorobenzene.

4,4 ‘, 4'-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate or mixtures thereof.

High molecular weight polyisocyanates are qu-ap-al-products of the reaction of diisocyanates and polyhydroxy compounds or polyamines. In addition, it is possible to use polyisothiocyanates of a lively mixture, polyisothiocyanates with polyisocyanates. Similarly, technical nor vinyl or crude polyisocyanates, e.g. crude methylene-bis - (- phenylisocyanahi) mixture.

In addition, in some instances, a prepolymer, i.e., an isocyanate component, is suitable. j. product after partial reaction of polyester polyol or a mixture thereof with diisocyanates. The type of diisocyanate used, resp. % of the polyisocyanate depends on the properties of the starting materials and the desired properties of the product.

The properties of solid (hard) polyurethane or polyurethane-isocyanurate foams are greatly affected by the type and amount of excipients, including: activators, stabilizers, emulsifiers, blowing agents, solvents, quenching agents, fillers and the like. (J. H.

Sautiders and K.C. Frisch: Polyuretban.es; Translation: Chimija polyurethane. Izdatelstvo „Khimija“, Moskva 1968.)

Particularly suitable activators are, in particular, tertiary amines, such as e.g. N, N‘-dimethylcyclohexylamine, dimethylethanolamine, triethylenediamine, dimethylaniline, pyridine, ethylmorpholine, quinoline, and the like. or an organic eye compound such as dibutyltin laurate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, mercuric acetate, antimony salts, bismuth, and the like. When using unrefined by-products, the catalytic influence of the metals present, in particular cobalt, chromium, manganese, molybdenum, iron and other transition metals, should be taken into account.

As trimerization catalysts suitable for the preparation of polyurethane isocyanurate foams, tertiary amines can be used (German Pat. No. 951161, U.S. Pat. No. 2,993,870, U.S. Pat. No. 856,372), trialkylphosphines (Hofmann AW: Jahresber 349 (1958), Ber, 3, 761 (1870)), organic onium compounds, ethylenimines, metal carboxylates, basic catalysts, including alkali and earth metal oxides and hydroxides, carbonates, alcoholates (V. Brit. Pat. 809 809) and phenolates, as well as alkali salts of enolizate-like compounds, tin compounds, antimony compounds, Friedel-Crafts catalysts and alkali metal chelates. Combinations of catalysts with a tertiary amine are well known (U.S. Pat. Nos. 3 J 30 846, 3 166 483, 3 189 626, 3 170 628

154,522, 2,993,870, 3,146,219; NSR pat. no. 1013-869), as well as organo-oxonium compounds (U.S. Pat. No. 837,120 and U.S. Pat. No. 3,010,963) and other catalysts.

However, only those having a concentration of 0.1 to 10 wt. allow trimerization of isocyanates at 20 ° C such that the conversion over 10 minutes exceeds 85 to 90 wt. Such catalysts include, in particular, 2,4,6-tris- (dimethylaminoethyl) phenol, 2,4,6-tris- (diethylaminomethyl) phenol, N, N ', N'-tris- (dimethylaininopropyl) -hexahydrothiazine, potassium hydroxide, hydroxide sodium, potassium acetate and combinations of a tertiary amine with an alkali.

Of the available blowing agents, those compounds which liberate gaseous compounds upon heating or conversion of the isocyanator are usually used. Low molecular weight liquids and water are preferably used in foaming. The heat of reaction and the reaction of water with diisocyanate causes foaming of the mixture to form a sufficiently stable foam that maintains its form until the mass has gelled. Suitable low molecular weight liquids are fluorochlorocarbons having a boiling point of about 20 to 50 ° C or mixtures thereof, e.g. trichlorofluoromethane, trichlorofluoroethane, dichlorodifluoromethane, dichlormonofluoromethane, monochloroethane, monochloronofluoroethane, difluoromonochloroethane or difluorodichloroethane. However, compounds can also be used

255 with a boiling point of -50 to 110 ° C, possibly with a higher boiling point (U.S. Pat. No. 2,865,969).

The stabilizers ensure the formation, size and uniformity of the foam cells. They are organo-transmitted, e.g. mixed polysiloxane-polyoxyalkylene polymers (U.S. Pat. No. 2,834,748 and U.S. Pat.

917 480).

The importance of emulsifiers is to improve the solubility of the reaction components or the auxiliary substances. Such are conventional emulsifiers, furthermore dioctyl phthalate, dibutyl phthalate and the like.

Bis- (1-alkyl) flame retardants may be added to the polyurethane or polyurethane isocyanurate foams. in particular, bis (2-chloroethyl) phosphate, bis (β-Bramethylphosphate), 2-chloropropane phosphate, and other organic compounds which act as a mentoring agent. Inorganic substances which also have the function of a filler and a colorant, e.g. ammonium phosphates, sodium borate, antimony trioxide, but also organic polymeric substances such as polyvinylchloride powder.

The process according to the invention can be carried out by known processes by pouring or spraying on conventional equipment used for the production of polyurethane compositions. Depending on the type of foaming device, the mode of dosing of the individual components is chosen.

Further details of the process for producing the inventive stage as well as other advantages are apparent from the examples.

Example 1

Štvcrhrdlej to flasks of 4 dm ^5, opaa nitrogen inlet were weighed 2530 g of distillation residues from the production of cyclohexanol and cyclohexanone by oxidation of cyklohaxánu (acid value 267.4 mg KOH / g, a saponification number of 420.2 mg KOH / g, a hydroxyl value of 4 95% by weight, bromine number 27.4 g Br / 100 g, water - 5.68% by weight, viscosity = 160 mPas (25 ° C, density d = ⁰ = 1,092 kg / m ³ ), 620 g pentaerythritol and 1,464 g of diethylene glycol, esterification and re-esterification with polyesterification at 200 DEG C. in the presence of nitrogen, while removing low-boiling products and water, yielded a product with an acid value of 1.8 mg KOH / g, saponification number 275, 0 mg KOH / g, hydroxyl value 500 mg KOH / g, viscosity 840 mPas at 25 ° C and density 1140 kg / m ^{3 The} prepared polyester polyol is mixed with a polyether polyol having a hydroxyl number of 450 milligrams KOH / g in a weight ratio of 3: 1. a mixture of polyester polyol and polyether polyol is suitable for sp It has a hydroxyl value of 488 mg KOH / g and is used to prepare a polyol having the necessary hydroxyl number.

Take Ό g of a mixture of polyester polyol and polyether polyol (3: 1 weight ratio), add the calculated amount of ethylene glycol to adjust the hydroxyl purity of the polyol to the desired value, as shown in Tab. First

Table 1

Purely an attempt Polyesterpolyol + + polyether polyol (3: 1) (g) ethylene glycol (G) Hydroxyl number of formulated oxygen component (mg KOH / g) 1 50 - 488 2 50 0.55 50? 3 50 1.1 517 4 50 1.65 533 5 50 ;? ;> 548 6 50 2 75 563

From these polyols (formulated oxygen component), a polyol component is prepared by admixing 1 g of VPFU polyurethane catalyst, 1,375.1 g of stabilizer B 8404 and 20 g of Freon 11. Adding a calculated amount of 4,4'-methanediphenyldiisocyanate (ur, Desmodur 44 Vj) to the prepared A rigid polyurethane foam is prepared and mixed by mixing them together with the following sequence (Table 2) and thermal stability (according to ASTM 1892).

Table 2

Number experiment MDI HO 1.5 J TZ Foaming times (with) SZ Λ7 epolytic stability 05 ^t! C ¹ 'in% 95 ° C 1 61 38 120, 120 0.30 0.80 2 63 38 115. 113 0.30 0.39 3 65 38 119. 120 0.20 00:29 4 67 40 120, 120 0,7 0 0.08 ABOUT 69 42 120, 120 0 08 0.3 0 70.5 42 120th HO hio 0.25

ΓΖ - start time, SZ - foam growth time, AZ - sticky loss

The foams produced have very good mechanical properties, low shrinkage at 85 ° C. Deň: 32 ° C.

Example 2

By mixing the polyester polyol described in Example 1 with polyether polyol (Slovaprcp

T 4:50] The acid value of 0.008 mg KOH / g, hydroxyl value of 450 mg KOH / g, a density of ³ dl = 1090 kg / m ^3, viscosity of / ^{25 to} 4.13 Pas is prepared as the base polyol of OH value 438 mg KOH / g. Addition of ethylene glycols to the basic polyol creates the new types of polyol, characterized in

Third

and b at 1 'k and 3

The attempt number 3? o 1 y o 1 polyester polyester] (gl '/ blood Hvhol P.8 ti) yéterpr- Ivo? ' (81 hydroxyl ČífmQ (mg KOH / g) 1 37.5 500 2 37.5 - 13.5 488 3 37.5 0.55 12.5 502 4 37.5 1.1 553rd 517 5 37.5 1.6 3 12 5 533 6 87.5 2 2 i 3., 5 548 7 37.6 2.73 13 j 563

T a b u I k a 8

Preparation of hard ¹¹ UR pony

The attempt number MDI (5) Times in the <1 TZ 5Z ΛΖ Non-foaming foams, thermal stability at 05 ^C, C; ·; · Zman? in % 2 01 33rd '10. 1 Ti 0.81 3 (33 · I. 0.39 4 65 38th T20- ,? G 00:29 5 67 40 I,.: 3, .12: 11 0.08 6 69 - * '50. '80 0.3 7 70.5 42 '0 ! > n 0.26

From these (Table 4), a polyol component is prepared by adding 1 g of VPPU-1375 catalyst, 1 g of Tegostab B 8404 stabilizer, and 20 g of chlorofluoromethane (Freon-11). The prepared polyurethane foam has an excellent structure, very good physico-mechanical properties, in particular thermal stability at 95 ° C.

Example 3

Four-necked flask to a volume of 2 dm ^3, fitted with a stirrer, a condenser and a nozzle, was weighed 258.0 g of the distillation residues of cyclohexanone by oxidation of cyclohexane, as specified in Example 1 and further 84.0 g of monoethylene glycol and 579.4 g of an aqueous solution, so . syrups from the production of pentaerythritol having a composition of: 8% by weight % pentaerythritol, 2 wt. % dipentaerythritol (hexose), 10 wt. % calcium formate, 3 wt. % pentaerythritol formate and 77 wt. water. The reaction is carried out at a temperature of 200 [deg.] C. with simultaneous removal of low-boiling fractions, in particular water. After 9 hours, when the acid value of the product = 1.5 mg KOH / g was reached, the reaction was terminated and the precipitate of calcium formate and / or the product was removed by filtration. pentaerythritol formate. 340 g of a polyether polyol having an acid number of 1.5 mg KOH / g, a saponification number of 280 mg KOH / g, a hydroxyl number of 470 mg KOH / g, a viscosity of - 920 mPas and a d4 of ²⁰ = 1 136 kg / m ^{3 are obtained} . The correction of the hydroxyl value to the desired value is done by adding glycerol to the values shown in Table 2. 5th

Polyester polyol (g) 50 50

Glycerol (gj - 0.8)

The resulting polyester polyol (mg KOH / g) 470 490

Table 5

50 50 50 50 50 16 2.4 3.2 4.0 4.8 510 530 550 570 590

From the polyol thus prepared, a poloyl component is prepared as described in Example 2 as follows: polyesterpolyol (with a content of glycerol = 40 g; polyesterpolyol (Uropol DP 124/0) in an amount of 10 g; catalyst S-26 - 0.05 grams) Catalyst Uropol DP 124/0 = = 0.25 g; Metation S-26 == 0.5 g; Trichlorofluorometon (Freon-11) = 16 g; Termolin 101 equals 5 grams; Tegostab B 8404 stabilizer = 1 g. This reaction with MDI in the amounts shown in Example 1 gives a rigid polyurethane foam with a very good structure and physico-mechanical properties.

Example 4

To 500 g of the polyester polyol prepared according to Example 1 having a hydroxyl value of 500 mg KOH / g is added 50 g of polyether polyol with a hydroxyl number of 48 mg KOH / g. The prepared polyol, a mixture of polyester polyol and polyether polyol, has a hydroxyl number of 458 mg KOH / g, corresponding to a desired value of 450 ± 25 milligrams of KOH / g. Then, the rigid polyurethane foam prepared by the process described in Example 3 has a uniform structure and very good physico-mechanical properties.

Example 5

Esterification and / or polyesterification of 425 g of distillation residues from cyclohexanone production by oxidation of cyclohexane with 72.5 g of pentaerythritol and 66 g of diethylene glycol gives 484 g of polyester polyol having a hydroxyl value of 213 mg KOH / g. After addition of 12 g of ethylene glycol, a polyester polyol having a hydroxyl number of 250 mg KOH / g is prepared.

2.2 g of Tegostab 1903, 0.6 g of a 10: 1 mixture of dimethylcyclohexylamine and dibutyltin dilaurate, 0.85 g of 2,4,6-tris (dimethylaminomethyl) phenol and 20 g of trichlorofluoromethane are added to 30 g of polyester polyol. After homogenization to a polyol component, it is mixed with 122 g of diphenylmethane diisocyanate. The resulting isocyanurate-modified polyurethane foam has a uniform structure and is self-extinguishing according to ASTM 1692.

Example 6

The procedure described in MS. AO No. 229 429 prepared polyesterpolyol from distillation residues · from the production of dimethyl terephthalate (acid number = 53 + 10 mg KOH / / g, saponification number = 488 mg KOH / g, viscosity at 50 ° C = 2 - 3.4 Pas), which after methanolysis had the following values: acid number = 96.5 mg KOH / g, saponification number = = 447.6 mg KOH / g, dynamic viscosity at 75 ° U = 0.8 - 5.3 Pas.

Weigh 750 g of distillation residue after methanolysis, 690 g of diethylene glycol and 100 g of pentaerythritol into a four-necked flask of 2 dm ³ , equipped with a stirrer, an adapter and a condenser. The reaction was carried out at ^200? C for 8 hours, and the polyester has an acid number = 1 mg KOH / g, hydroxyl value = 420 mg KOH / g, saponification value = 249.3 mg KOH / g and a viscosity of 14.4 Pas equal . The polyol component is prepared from 5Ό g of polyol, 1.1 g of ethylene glycol, 1 g of catalyst VPPU 1375, 1 g of stabilizer B 8404 and 20 g of trichlorofluoromethane (Freon 11). Reaction with 58 g of MDI produces a rigid foam with uniform structure and good physico-mechanical properties. Example 7

A polyester polyol having a hydroxyl number of 213 milligrams of KOH / g was prepared according to the procedure of Example 5. After addition of 12 g of a 1: 1 mixture of methanol and monoethylene glycol, a polyester polyol having a hydroxyl number of 250 mg KOH / g is prepared.

To 30 g of treated polyesterpolyol (OH equals 250 mg KOH / g) was added 2.2 g of Tegostab 1903 stabilizer; -tris- (dimethylaminomethyl) phenol and 20 g of trichlorofluoromethane After homogenization to a polyol component, 122 g of diphenylmethane diisocyanate are mixed, the resulting isocyanurate-modified polyurethane foam has a uniform structure and is self-extinguishing according to ASTM 1692.

Claims (1)

SUBJECT Process for producing polyurethanes and / or polyether polyols preferably for producing polyurethanes and polyurethane or polyurethane-isocyanurate foams from compounds with a non-conforming hydroxyl number, preferably containing the necessary additives such as activators, stabilizers, emulsifiers, blowing agents, FIELD OF THE INVENTION Flame retardants, catalysts, fillers, dyes, characterized in that 0.1 to 15% by weight of the basic polyol having a hydroxyl number of 30 to 800 mg KOH / g is added. compounds with at least 1 active hydrogen having a hydroxyl number of 20 to 2000 mg KOH / g.