CS201229B1 - Process for preparing elastic microcell foamed polyurethanes - Google Patents

Description

The object of the invention is to produce elastic, micro-cellular polyurethane compositions by means of catalyst systems at relatively short initial times and after a short residence time in the form of:

To a mixture of polyester alcohols, chain extenders, dispersants, triethanolamine, cell size regulators, physical or chemical blowing agents, a mixture of 1,4-diazabicyclooctane and dimethylcyclohexylamine is added to accelerate the reaction of these materials with the isocyanate. The ratio of 1,4-diazabicyclooctane to dimethylcyclohexylamine is 1 part by weight to 0.8 to 5 parts by weight, preferably 1 part by weight to 2 parts by weight

The polyurethane integral foams produced according to the invention are used, for example, for shoe soles, technical moldings in the manufacture of vehicles and in mechanical engineering and in orthopedic technology.

The invention relates to a process for the production of elastic, micro-cellular polyurethane integral foams which are used, for example, for shoe soles, technical moldings in vehicle production, as well as in mechanical engineering and orthopedic technology.

It is known to produce elastic, microcell polyurethane integral foams using tertiary amines such as 1,4-diazabicyclooctane, morph2012 derivatives.

201 229 liner and dimethylbenzylamines. These amines are often combined with an organic acid salt and divalent and quaternary tin to reduce the retention time of the foamed molded part. hydrolysis · Tertiary amines without catalyst addition do not allow very short residence times in the mold, or only when very short L start times are to be expected ·

Cílem- invention is to taicový kata of ^{Ly s} s ^y Torr hundredth that allows to create j ^Iz the shortest time during relatively long periods of initial elastic mLkrobuněčné integral foam and simultaneously reducing the sensitivity of polyurethane integral foams to hydrolysis.

The object of the invention is the production of moldings of elastic · microcellular, polyurettenovýoh integral mass of foam with relatively long starting time and a short "residence time as · Úcol is ^DDRESSING invention ^t and that the mixture ^{of p} olyesterovýc ^h alcohols, for ^ užovačů chains dispersants , trietaanobmin, cell size regulators, physical and / or chemical blowing agents, a mixture of 1,4-diazaiicylooctane and dibethylcyclohexylamine is added to accelerate the reaction of these substances with the isocyanate.

The invention therefore provides a process for producing elastic and Mkrobuněčnýoh polyux e ^ ^^ ^^ button ^ x v ^ y OH integral foams of components A, sestávaaící polyester alcohols, extenders, dispersants, treθtaanolťminu regulators velikoosi cells to physical or chemical ^d žuvaclel ^and from ^ .s žty b consisting of MO-agement ^4, 4 - ^{bis DFE} lIyr ^tt andiisžkyanátuj invention consists in that the component a is added to a mixture of 1,4-diazaiicyilžoktanu and di ^ C ^ eth The cyclohexylamine, wherein the .beta.-diazabicyclooctane and the dibettylcyclohexylamine are added in an instantaneous ratio of 1 to 0.8 to 5 parts by weight, preferably 1 to 2 parts by weight, and wherein the concentration of the mixture in component A is 0; 15 to 5% hmoonoot ·

With the present invention, elastic, microcell polyurethane integral foams can be produced with very short residence times in the mold. Surprisingly, the composition according to the invention is substantially higher. acceleration of growth of predominantly linear moles of foam foam than would be expected from the sum of the individual efficiencies · Adipic acid condensation products with ethylene glycol, prpa-1,3-dioleb, prpa-1,2-dioleb, iutane-1 are used as polyester alcohols, 4-Dissolve, hexane-4-diol and a molecular weight of 2,000, singly or as above.

Ityllinglycol as well as butane-1,4-diol are preferably used as chain extenders.

Dispersants are, for example, castor oil sulphonates in aqueous solution.

Special silicone-based products are used as cell size regulators.

While a chemical blowing agent is usually used carbon dh.ičitý- isokytanátu from reaction with water, the physical blowing agents are in most cases halogenated hydrocarbons such as beelh ^г leniCtorid, trLJLUužrtrCohlorettai, moa01uootrichloзmettai or jejloh · 3-201 229 mixes SMOS The polyester alcohols, chain extenders, dispersants, cell size regulators and blowing agents are added according to the invention a mixture of 1,4-diazabicyclooctly and dimethylcyclohexylemine and homogeneously by intensive defrosting * This mixture forms component A and is stable for several months *

Component A is reacted to obtain an elastic, microcrystalline polyurethane foam with component B, moiified 4,4-dipherylmethanediisolyianetide. Component A is preferably a mixture of up to 90 parts by weight of polyester alcohol, mol * by weight 2,000, up to 16 parts tmoo. elongated strings

0.2 to 0.7 parts tmoo. triethanolemine;

0.1 to 0.3 parts by weight of the cell size regulator,

0.05 to 0.25 parts by weight of sulfonated castor oil, up to 7 parts by weight of trilluorotecohlorolamine,

0, up to 0.5 parts hmoo. water,

0.1 to 1.0 parts by weight of 1'-diazabicyclooctane a

0.1 to 2.0 parts tmc. limettyloyclohexylamiou.

This component A is reacted with component B, and preferably the following composition:

up to 50 parts hmoo. polyester alcohol, mol * tmoonnosi 2,000 and up to 50 parts by weight * 4,4 * »0ifo! ^et tmothin ^KKI anlátarótu _t the portion 4.4 ** olifelettaothitkkiaolátanátu being liquefied by the heat treatment or katalyticýó. The polyester alcohol may be identical to that which has been killed in component A or may be different. Intensive mixing of components A and B, and adding this mixture to wipe lubricant ^io é. Wavre ^ s and at a temperature of 40 ^{from 0} ° C for 7 olňá-metallic ^{and thus} is made of an elastic výHs ^, Okroporézní polyuretianová integral foam Ьо у ^, which can be already removed after two minutes from the mold without difficulty.

Examples:

Example 1

Component A consists of t

81.90 parts hmoo. polyester alcohol mol. tmooncosi 2 000 from adipic acid, ethylene glycol and liettyleoglicol,

13.10 parts hmoo. ettyleoglikol,

0,50 parts by weight of triethanol ethanol,

0.15 parts hort. si.lkknt ^ <^ v ^ é ^ ^ o oils,

0.13 parts by weight of sulphonated castor oil,

5.00 parts hmoo. trilluortikchkorotlaou,

0.26 parts hmoo. 1,4-thiazabicyclooctane a

0.50 parts hmoo. of limettyliyclohexilamine is reacted with component B consisting of

201 229

35.90 parts by weight polyester alcohol which is identical to ПиО, which is used in component A,

15.90 parts by weight of liquefied α, β-di-di-methyl methandlifloocyanate, and

48.10 ddl tanot. 4 * 4'-ddfeiylmrthanniisokyuntu ·

The isocyanate index is 100.

By mixing the components A and B and introducing the mixture into a lubricated, sealed and 40 to ⁷⁰ ° C oily metal foil, an extruded polyurethane integral foam molding of the following properties is obtained »

Initial conquer 12 p Form residence time 120 e Density of loosely foamed matter 200 kg / m ³ Hiuitota in the form of foamed matter 550 kg / m ³ Elongation at break 350% Tensile strength 4.2 MPa

Resistance to tearing 188 N / cm

Example 2

81.96

Component A consisting of parts by hours

12.80

0.50

0.15

0.13

5.00

0.26

0.50 parts parts parts parts parts parts parts mass.

wt.

wt.

wt.

wt.

wt.

wt.

polyester alcohol mol. 2,000 of adipic acid, glycol and diethylene glycol, di, ethyl englycol, trihiolimine, silicone oil, sulfonated castor oil, trifluoromethylchloroethane, 1,4-diazabicyclooctane and dimethyloycloihixylaine are reacted with ethylene to form the reaction with ethylene. zt

35.90 hmoo parts. polyester alcohol mol. masanos! 2 000 from adipic acid, ethylene glycol and dienhylinglyl,

15.90 part ^{of the} HMO. zkapalróróho 4,4 ⁱ · ⁿ ife: ^it lmnthistliisnkyадát a

43.10 d ^d L ⁱⁿ IHM-t, ^4,4 'diphenyl lmlt ^{y] n} Ьal iiso] ς ^y l ⁿ here.

Isocyanate index Siní 100.

Intensive mixing of components A and B and incorporating a lubricant into the Soos mopping, and concluded .ípI Lu-40 and ⁷⁰ ° C, th old & zínkáró metal mold molding of an elastic, polyurethane integral foam 'following properties »

Initial conquer

The residence time in the form of s

120 s

- 5 201 229

Free foam density 23 ° kg / m ³

Huuteta in the form of foamed material 540 kg / m ³

Overload elongation 330%

Tensile strength 2.99 MPa

Tear resistance 188 H / cm

Example 3

Component A consisting of:

77.44 parts.hmoo * polyester alcohols mol · hmoonooti 2,000 of adipic acid, ethylene glycol and diethylene glycol and adipic acid, ethylene glycol and hexane-1,6 diol,

15.50 parts hmcrt · dutan-1.4vdiolu.

0.50 parts by weight * of triethanolamine,

0.15 parts of hmoo-tilkonne oil,

O., 13 parts by weight of sulfonated castor: linseed oil,

5.00 parts of hmoo · trifluorotetrachloride,

0.05 parts by weight of water,

0.36 parts of hmoo-1,4-diazabicyclooctane and

0.50 parts by mass of oimethyloyclohylylin reacts te with component B consisting of:

35.90 parts of hmoo · polyester alcohol mol · 2,000 of adipic acid, ethylene glycol and diethylene glycol

15.90 parts of hmoo * liquefied 4,4 * -difluoromettaodiisocyanate, and

48.10 parts of hmoo * 4 _t 40-dinenmlπlttlnoldiocoyanate _β

The isocyanate index is 100 ·

Intensive mixing microns tložek A and B and incorporating this tměei into lubricant mopping closed and te ^p Lot 40-70 ° C for times ^to ovové ^formyl te ^l y ^{ka howling even to} a elastica, Mito-orézní , polyurethane, integral foams of the following properties:

Initial time p

Dwell time in the form of 100 t

Bulk density ²²⁰ kg / ^m3

HuSota in the foaming foil 55 ^{0 k} g / ^{m 3}

Potential elongation at overload 360%

Tensile strength 5.60 MPa

Oddness for those further tearing 182 N / cm

Example 4

Component

77,44 parts

15.50

0.50

0.15

0.25

5.60

0.10 parts parts parts parts parts parts

And consisting of:

polyester alcohol molar mass of 2,000 glycol and butane-1,4-diol butane-1,4-diol, triehanolimine, silioone oil, sulphonated castor oil, trifluorotrifluorethane, water, w / w w / w w / w w / w mass #

0.20

0.40 is reacted with component B consisting of:

parts parts hmoo # mass #

1,4-diazabicyclooctane and dimethylcyclohexyXamine,

35.90

15.90

43.10 parts hmoo «mol alcohol polyester # 2000 hmotnooti glycol and diethylene parts ^ 0 ^ LA alněné ^{p h} o _l 4 * 4" ⁰ ifoJ ^eth mothan ^t iiso ^s yunátu parts ηο ^ ^ 4.4 * - ^for ifθI ^it ldiiso ^á yanátu ♦ tyseliny adipic acid, adipic ethylenethylenIsokyanátový index is 100 * closed

Intensive mixing of components A and B, and introducing the mixture into a lubricant mopping, and ^t e ^pl of ^T u 4 ^{0-7 0} C edges of the metal mold from ^ ^{ka and} the molded part of resilient ^ kroporézní polyurethane integral foams following properties »

Initial time:

E

Dwell time in the form of 120 s

Bulk density of ²²⁰ kg / m ³

Density in the form of foamed material 55 ^{0 kg} / m ³

Slight elongation at break 360%

Tensile strength 5.60 MPa

Resistance to tearing 182 N / cm

Example 5

Component A consisting of i

77.44 parts by weight of polyester alcohol moo · 2000 weight of adipic acid, ethylene glycol and butane-1,4-diol,

15.50 parts by weight of butane-1,4-diol,

0.50 parts hmoo # trtehaniolamine,

0.15 parts by weight of silicon oil,

0.25 parts of wtt # sulphated riono oil,

5.60 parts of hmoo # trfΓluortrChhtorehløou,

2U1 229

0.10 parts by mass, water,

0.20 parts of hmoO · 1,4-diazabicyclooctane a

0.40 parts of hmoO * dimethylcyclohexylamine is reacted with component B consisting of:

30> 90 parts of a polyester alcohol hmoo * * moo hmoonoosi 2000 from adipic acid, ethylene glycol and diethylene glycol ΐ5, θ ⁰ part ^{of the} HMO ztapalněn · ^ he ^ fenyl.metbandid.sokyanátu and 4,4-

4β, 10 dW mass · 3,4 * - ^d ifei ^y rloe ^th andi ⁱ sok ^y anate ·

The isocyanate index is 100 *

Intensive mixing of components A and B, .and introducing this mixture into mLzadlem mopping, ^é closed and at 4 ° ^and 70 ° C vyiwá-metal fomy the ZIS ^{Ka and} the molded elastic Mkroporézní polyurethane integral foams following features!

Initial time p

Form residence time 120 s Goose for those loosely foamed matter 180 kg / ^np Huusota in the form of foamed matter 550 ^{kg /} n ^p Elongation at break 350% Tensile strength 5.0 MPa Resistance to further tearing 192 N / cm

Example 6

Component A consisting of t

37 * 44 parts hmoo * polyester alcohol mole, halo o c: L 2,000 and adipic acid and ethylene glycol,

45.50 parts of 1,4-diol hmoo _e butane,

0.50 parts of hmoo · triethanolminine,

0.15 parts of hmoo · silion oil,

0,25 parts of hmoo * sulphonated castor oil,

5.60 parts hmoo *

0.10 parts by weight of water,

0.20 parts of hmoo · 1,4-diazabicyclooctane a

0.40 parts by weight of dioethylcyilohexylamino, is reacted with component B consisting of:

35.90 parts by weight of the polyester alcohol molarity 2000 of adipic acid-thylene glycol and diethylene glycol,

15.90 parts by weight of liquefied 4,4 &apos; -dolyollo-di-diisulfate and

⁴⁸ 1 ⁰ parts * l ^ e ^ mo -dttenydilsotyarótu

Isocyanate index is 100 *

201 229 “ ⁸ ”

Intensive mixing of components A & B, and introducing this mixture into swabbed lubricant, ^and an enclosed tepl.otu 40-70 ° C oitfátá tovová tnmy ^f is obtained by molding of an elastic, microporous polyurethane integral foams following properties:

Initial time 12 p Form residence time 120 s Hiutota of freely foamed matter 200 kg / year ³ Huuttta in the form of foamed matter 550. kg / m ³ Elongation at break 340% Tensile strength 5,42 MPa Resistance to further tearing 191 N / cm

Example 7

Component

77,44 parts parts parts parts parts parts parts parts parts

And consisting of:

a blend of polyester alcohol mot, weighing 2,000 from adipic acid, ethylene glycol and diethylene glycol, and from adipic acid, ethylene glycot and heran-1,6 *> diol, butane-1,4-diol, silktone oil, sulphonated castor oil, trifluorotrichltrethaou, water,

1,4-0iazabityklotktaou a

Oimethyloyclohexylam.eu, mass · mass · mass · mass.

mass * mass · mass · mass *

15.50

0.50

0.15

0.25

5.60

0.10

0.20

0.40 is reacted with component B consisting of i

35.90 parts by weight · polyester alcohol mol · weight 2,000 from adipic acid, ethylylene glycol and diethyleoglyl,

15.90 parts by weight · fluidizing it ^ 4,4 '- ^y DIFOU rloethaediiso ^to yaeátu and

43.10 parts by weight · 4,4 -d ¹ · lmetaιeddiSoikyonátu diones ^l.

The isocyanate index is 100 «

Intensive mixing of components A and B, by introducing the mixture into a lubricant mopping, closed), and n ^s and a temperature of 40 ° ^≧ 7 ° C dial ktvtv the ^E form of i ^ Toray Molding of Elastic m.kroporéznt, ptlyurethantvé, these integral foam Properties:

Initial time 14 s

Dwell time in the form of 120 s

Hustota_volně.zpěeěe ^s of the mass 240 kg / m ³

Hutota ftime in back ^{of EE E} E ^E toot 550 ^kg / m ³

Elongation at break 330%

Tensile strength 4 »91 MPa

201 229

Ϊ́άοΐαοβΐ against further tearing 212 'N / am,

Example 8

Component A consisting of:

76 * 64 parts by weight of polyester alcohol mol · hlOnooti 2000 from adipic acid, ethylene glycol and diethyleoglycol,

15.50 parts by weight · butadiene] n-1, _t 4 _t-diol

0.50 parts of hmoo · triethnoolmiou,

0.15 parts of hmoo-thioioon oil,

0.25 parts by weight of water,

0.25 parts by weight of 1'-diazabicyclooctane

0.50 parts by weight Dimethylcyclohexylamine reacts with component B consisting of:.

35.90 parts of hmoo, polyester alcohol mol · hmoonoosi 2000 from adipic acid, ethylene glycol and diethyleoglycol,

15.90 ^d clay ⁱⁿ compositions ztepalošráho h _j, ^4'about IFO ^{Oi et} tmothyn ilo]; ^t anatum

43.10 ddl Ih ^ o. 4444 difeoylmeeihaidiisolkfyaotu.

Isocyanate iodex Uioi 100 ·

Idtenzivním trácháním components A and - B vdeteoϊm this mixture into lubricant vytřeoé, uzavřeo ^é OA - ^t ep ^l ol 4 ° and #., 70 ° C vylwá ^ ^k ovové forms of ^ TOV ^ howling ^{even to} a ellstic ^IÉ · milkro ^p orézní polyurethadové · · iotegráloí pěoové matter ohledujících vlastoostí:

PdčáteUoí doba 12 p The residence time in the mold 120 s voloě zpděně hmo ^ ty ² 40 kg / m ³ Density - in the form of foamed matter 550 kg / m ³ Relative elongation at break 360%

Tensile strength 5.01 MPa

Resistance to the next 198 N / cm

Claims (1)

A process for the production of elastic, microcrystalline polyurethane polyurethane foam compositions of component A, consisting of polyester alcohols, chain extenders, dispersants, cellulose regulators, cell size regulators, physical and / or chemical agents. l ^ il. · B and from složty consisting -of mo ^OIF and ^also it OVLD ^s · h ⁴ * - ^d ifoI ^{av ett} ldthat ld] ¢ ^t utótu, vyzroaující in that the component a - is added a mixture of 1 · 4-thiazabicyclooctlyl and dimethyldiocyclohexylamine, wherein the 1,4-thiazabiryclooctad and iimattylcyilohexyllmid are added in a ratio of 1 to 0.8 parts by weight, preferably 1: 2 parts by weight, and wherein the concentration of the mixture in the component And 0.15 to 5% by weight of mono-osioids.