FR2491075A1 - METHOD FOR MANUFACTURING MOLDED SOFT MOLDED POLYURETHANE PRODUCT - Google Patents

Abstract

THE PROCESS IN ACCORDANCE WITH THE INVENTION IS CHARACTERIZED IN THAT A POLYOL, A POLYISOCYANATE, WATER AND A CROSS-LINKING AGENT, CONSTITUTED BY AN ADDITIONAL PRODUCT TO L ETHYLENE OXIDE OF A MANNICH CONDENSATION PRODUCT PREPARED BY REACTION OF NONYL PHENOL, DIETHANOLAMINE AND FORMALDEHYDE. VERY LIGHTWEIGHT FOAMS ARE OBTAINED, WHICH FOUND APPLICATIONS IN THE AUTOMOTIVE INDUSTRY AS ENERGY ABSORBING PRODUCTS AS WELL AS IN OTHER INDUSTRIES.

Description

The present invention relates to the production of

  The particular crosslinking agent, the use of which has proved advantageous in the semi-flexible energy absorbing foams of the invention, has been described as a detergent in the US Pat.

United States of America 2,998,452.

  U.S. Patent No. 4,137,265 describes the product of the precursor Mannich condensation of the crosslinking agent of the invention. A polyol which is a propylene oxide adduct of the precursor Mannich condensation product for the preparation of rigid polyurethane foams is disclosed and claimed. In U.S. Patent 4,137,265, there is described

  and claims the adduct to the oxide of

  nonyl phenol, formaldehyde and

  ethanolamine. This product is useful as a polyol for rigid foams. We discovered

  surprising that the adduct to ethylene oxide

  Mannich condensation product was particularly advantageous in formulations for

semi-flexible foams.

  In the automotive industry in particular, new technologies are constantly being developed to increase the safety of vehicles while reducing their weight. One of the main safety research topics in the automotive industry is the use of molded polyurethane foams that absorb the energy released during an impact. The present invention relates to an improved process for producing molded polyurethane foams which, in addition to absorbing the energy of the shocks, are lighter, which leads to a reduction in the weight of

vehicles.

24910 75

  The invention relates to a process for the preparation

  molded flexible polyurethane product.

  characterized in that a polyol, a polyisocyanate, water and a crosslinking agent consisting of an ethylene oxide adduct of a product of the invention are reacted in a sealable mold. Mannich condensation prepared from nonyl phenol, diethanolamine and formaldehyde. The invention also relates to a product consisting of polyurethane

  molded flexible obtained by the method mentioned above.

  When molding products based on poly-

  urethane, the reaction mixture is introduced into a rigid mold sufficiently strong not to deform when it is subjected to the pressure that is established when the expansion reaction occurs. This mold can be made of metal, plastic, wood or other materials and combinations of materials. In practice, the mold must be strong enough

  to support the pressure of the molding and must also

  allow a sufficiently tight junction so that the reaction mixture is not expelled from the

  mold during the expansion process of the foam.

  We introduce into this preheated mold a

  sufficient amount of the polyurethane reaction mixture

  expansive thane of the invention to obtain an excess

  muffle filling from about 10% to about 20%.

  The term "excess mold filling" refers to the amount of expandable reaction mixture that is

  greater than the quantity needed to fulfill exactly

  the mold once the reaction is complete. The

  plaintiff uses in practice an excess of

  pleating from about 10% to about 20%. A greater excess of filling can be used with very strong and hermetically sealed molds, which would tend to increase the density of the foam.

249 1075

  This excess filling and the use of a hermetically sealed mold in combination with the reaction mixture of the invention results in compaction of the polyurethane foam and provides an improved cell structure substantially free of voids as well as better skin quality. of the final product. After foaming the product, it is allowed to stand in the mold for about three to nine minutes, with additional external heat input not usually required to cure the product. The curing time can of course be

  longer but this is not usually necessary.

  At the end of this short curing period, the product is removed from the mold and an article is obtained.

  of flexible polyurethane having a

  essentially with open cells, satisfactory skin quality and practically

free of voids.

  In the one-step process of the invention, the polyether polyol, the organic polyisocyanate, the water, the crosslinking agent and a catalyst are all introduced simultaneously into the mold where they react, foam and cure without it is necessary to use an additional operation

  hardening at high temperature.

  Polyether polyol (and not the crosslinking agent

  culation) can be a polyol having a functionality of about two to about six and an equivalent weight of 1600 to about 2000 and

  containing about 80 to about 100% of hydro-

primary xyls.

  The polyether polyols which can be used in the present invention are prepared by a well-known process which involves the reaction of the polyhydroxylating agent, such as ethylene glycol, propylene

  glycol, a low molecular weight polypropylene glycol

  trimethylolpropane, glycerol, 1,2,6-

  hexane triol, sorbitol, pentaerythritol, etc., or mixtures thereof, with a lower alkylene oxide such as propylene oxide and butylene oxide, mixtures thereof, or mixtures thereof ethylene oxide with propylene oxide and / or butylene oxide. This reaction is carried out by

  a well-known method using a catalyst of

  coxylation which is generally an alkali metal hydroxide such as potassium hydroxide. The reaction is continued until the product having approximately the desired molecular weight is obtained. It is then necessary to react the product prepared as described above with ethylene oxide to obtain the desired degree of primary hydroxyl end groups in the polyether chains. This process is described, for example, in the US Pat. No. 3,336,242. The percentage of primary hydroxyl end groups in the polyether chain is generally increased by the addition of ethylene oxide alone; however, it will be appreciated that this result can also be achieved with ethylene oxide mixed with certain proportions of propylene oxide. It is also within the scope of the invention to use a polyether polyol which may comprise sequences of various alkylene oxides in the molecule and not to limit these sequences.

  ethylene oxide only at the terminal positions.

  Although polyether can be used

  polyols of higher functionality, it is preferred to use

  polyols having molecular weights of from about 3,500 to about 4,400 and containing about 80% or more of primary hydroxyl groups, which are

  for example, addition products to the oxides of alcohols

2 4 9 1 C 7 5

  kylene of a mixture of glycol and a triol.

  It is particularly preferred to use a polyol having a molecular weight of about 3 900-4000.

  consisting of a product finished with oxide of

  ethylene obtained by addition to propylene oxide of a mixture of a polypropylene glycol with a molecular weight of about 400 and a propylene oxide adduct of glycerol having a molecular weight of about 700. The percentage of primary hydroxyl end groups in this polyol is

greater than about 80%.

  The organic polyisocyanate is preferably an aromatic or aliphatic organic polyisocyanate such as 3,3'-dichloro-4,4'-biphenyl diisocyanate, diphenyl diisocyanate, ethylene diisocyanate, propylene-1,2-diisocyanate, and the like. , 4-tetramethylene

  diisocyanate, p-phenylene diisocyanate, 2,4-

  and 2,6-toluene diisocyanates, o, o'-, o, p'- and p, p'-

  diphenylmethane diisocyanates, hexamethylene diiso-

  cyanate, polymethylene polyphenylisocyanate and

mixtures thereof.

  Most preferred for the

  implementation of the present invention, polyiso-

  Organic cyanates obtained by phosgenation of the reaction product of aniline and formaldehyde having a functionality greater than or equal to 2.2. Although functionality of about four or more is possible, it is not convenient to obtain them by known methods. It is preferred to use isocyanates having functionalities from about 2.2 to about 3.5.

  the particularly preferred range being from 2.2 to 2.8.

  Useful isocyanates are prepared by

  generation of amine precursors obtained, for example, by the process described in the US Pat.

  United States of America 2,683,730 and 3,362,979.

  The foams according to the invention also contain a crosslinking agent which is the product

  addition to ethylene oxide of the product of the con-

  Mannich densification of nonyl phenol, diethanol-

  amine and formaldehyde. The preparation of this Mannich condensation product is described in US Pat.

  United States of America 4,137,265.

  To this product of Mannich condensation, ethylene oxide is added in such a quantity that adducts with hints are obtained.

  of hydroxyl from 230 to 500 (in meq of KOH / g of sample).

  The preferred amount of ethylene oxide gave an adduct having a hydroxyl number of

  470-480 (in meq of KOH / g of sample).

  The polyol component is mixed with the

  organic isocyanate to the reaction mixture in such proportions that the ratio of isocyanate groups to hydroxyl groups, generally known as the isocyanate index, is from 0.85 to about 1.05, the isocyanate index particularly preferred being about 0.95. The group report

  isocyanates containing hydroxyl groups includes water which may

  present in the expansible reaction mixture as well as the hydroxyl groups present

  in the crosslinking agent of the invention.

  Water is used to produce the blowing agent and / or to adjust the density of the foam when practicing the invention. The use of the crosslinking agent of the invention has the advantage of making it possible to use a larger amount of

  amount of water without affecting the quality of the foam.

  It is preferred to use about 2.5 parts by weight of water per 100 parts of polyol and it has been found that the best results are obtained when the amount of water is in the range of about 2.2 to about 4, 5 249 1lC5

  parts by weight per 100 parts of polyol.

  Catalysts useful in the present invention may be those normally used in polyurethane foams, such as tertiary amines and organometallic compounds. Specialists will be able to choose a system

catalytically appropriate.

  By way of example, useful tertiary amines may be trialkylamines (such as

  trimethylamine, triethylamine), heteroamines

  cyclic such as N-alkylmorpholines (such as N-methylmorpholine, N-ethylmorpholine, etc.), 1,4-dimethylpiperazine, triethylenediamine, etc.,

  aliphatic polyamines such as N, N, N ', N'-

  tetramethyl-1,3-butanediamine. The catalysts employed in the examples below can also be used. Although the improvement is observed with various catalysts, the two-mole propylene oxide adduct of the

dimethylaminopropylamine.

  As organic tin compounds used as catalysts and particularly suitable for the preparation of flexible foams, there may be mentioned a stannous or stannic compound such as a stannous salt of a

  carboxylic acid, a trialkyltin oxide, a dihydrogen

  dialkyltin ethylene oxide, dialkyltin oxide, etc., organic groups of the organic part of the compound

  of tin being C1 to Ca hydrocarbon groups.

  By way of example, it is possible to use dibutyltin dilaurate, dibutyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide, and stannous octoate. stannous oleate, etc., or a

mixture of these.

  The catalysts that can be used in the preparation

249 1075

  The polyether polyurethane foams described herein are used in a proportion of about 0.05 to about 2.0% by weight based on the combined weight of the hydroxy compound and the polyisocyanate. It is preferable that the amount of catalyst used is

from 0.1 to 1.5% by weight.

  The catalysts involved in the present invention can be used alone or mixed with one or more other catalysts such as other tertiary amines, or with another organic compound of the present invention.

  tin or other polyurethane catalysts.

  If desired, other conventional formulation ingredients such as foam stabilizers also known in the art can be used.

  names of silicone oils or emulsifiers. The sta-

  The balance of the foam may be a silane or an organic siloxane. For example, compounds having the formula RSi [O - (R SiO) - (oxyalkylene) R 3 can be used; R is a C 1 -C 4 alkyl group; n is an integer of 4 to 8; m is an integer of 20 to 40; and wherein the oxyalkylene groups are derived from propylene oxide and ethylene oxide. See for example

  U.S. Patent 3,194,773.

  The use of an additional inert blowing agent such as a gas or a releasing product

  gas, is within the scope of the present invention.

  For example, halogenated hydrocarbons may be used

  low boiling point such as trichloromonio

  fluoromethane and methylene chloride, carbon dioxide, nitrogen, etc. The inert blowing agent decreases the amount of isocyanate and excess water that is required in the preparation of the flexible urethane foams. Specialists can choose the right expansion agent. We will be able

2491C75

  example refer to the patent of the United States of America

3 Q72 082.

  As shown in the examples below, it is advantageous to use the present crosslinking agent which consists essentially of a pentol, in combination with other low molecular weight products containing hydroxyl groups.

  and having hydroxyl numbers of about 200 to 2,000.

  For example, low diols have been found

  molecular weight such as ethylene glycol,

  pylene glycol and dipropylene glycol as well as carbamate diols and difunctional amine polyols were usable, as shown in the examples

  XI-XV below Other similar products are also

  may be used in association with the

crosslinking of the invention.

  In the following examples, the present invention and the numerous improvements will be described.

  made by the crosslinking agent of the invention.

  However, many of these improvements are

  a more subjective character and can not be demonstrated by objective tests recognized in the art. The applicant has found that the use of this crosslinking agent in semi-flexible foam formulations brings many improvements and advantages among which:

  (1) a significant improvement in the characteristics

  moldability tests, (2) better material utilization efficiency (lower density foam), (3) reduced voids in castings, (4) improved processability

  and less sensitivity to the conditions of

machinery,

249 1,075

  (5) excellent cell structure and uniform appearance,

  (6) excellent adhesion to vinyellow skins

  used for molded parts, (7) a significantly improved water use latitude,

  (8) better hardening characteristics

  (9) a lower content of closed cells, which leads to a non-shrinking foam, (10) excellent compatibility of the entire formulation, allowing uniform treatment . The following non-limiting examples are

  given by way of illustration of the invention.

EXAMPLE I

  Preparation of the crosslinking agent A Mannich condensation product is prepared from 1.0 mole of nonylphenol, 2.0 moles of diethanolamine and 2.0 moles of formaldehyde and the water is removed by vacuum purification. (see

  U.S. Patent 4,317,265).

  To 28.032 kg of the purified Mannich condensation product, introduced into a 68.1 liter boiler and heated to 1150 ° C., 11.567 kg of ethylene oxide is added at 115.degree.-12.degree.

  1 hour 20 minutes. The reaction mixture is digested

  at 1100C for an additional 1 hour 10 minutes. Unreacted oxide is removed by vacuum purification and the product is collected after cooling. The viscosity of the product is 210o cps; the water content is 0.05%, the hydroxyl number is 475. This product will be referred to as the crosslinking agent A and is the

crosslinking of the invention.

1 1

EXAMPLES II - V

  These examples illustrate the use of

  the crosslinking agent as crosslinking agent

  unique in formulations for semi-flexible instrument panel foam. These sectional flows are the initial flows made to determine the nature and behavior of the expansion.

  of this material. In these examples and the examples

  Then, the constituents are weighed into a paper cup 12.7 cm high, mixed with stirring; a product available on the market under the name of "MONDUR MR" is added, the mixture is vigorously agitated and poured into a second 12.7 cm cup and then the foam is allowed to stand and rise. Climb time c

  foam = time in seconds for the foam to reach

  the top of the cup. Time of disappearance of stickiness = time in seconds at the end of which the surface of the foam comes off when with an object such as a tongue depressor or a probe pencil. Formulation, parts by weight

"THANOL SF-39501"

Crosslinking agent A Water

"THANCAT DME"

"THANCAT DPA3"

  Carbon Black Paste Constituent A

"MONDUR MR"

  Cross-section tests Foam rise time, s Stickyness disappearance time, s Height in section, cm Weight of cut, gram II, 0, 0 2.2 2.0 47.0 III, 0 8.0 2.5 1.0 2.0 IV, 0 8.0 2.5 1.5 2.0 V, 0, 0 2.5 1.2 2.0

49.0 49.0 45.5

17.2, 8

756

17.0 76.6 17.5 71.3

2 4 9 1 G0 7 5

  (1) an ethylene oxide terminated product obtained by adding to propylene oxide a mixture of diol and trihydroxyl initiators with a molecular weight of about 3,950, produced by the

TEXACO CHEMICAL CO.

  (2) N, N-dimethylethanolamine, produced by

TEXACO CHEMICAL CO.

  (3) adduct with two moles of oxide

  of propylene dimethylaminopropylamine.

  (4) polymethylene polyphenylisocyanate, produced by Mobay Chemical Corp. (5) height in section = total height of the mounted foam when it has reached its final height. Weight of the cut = weight of the foam in the cut after cutting the top of the foam flush with the edge of the cut. This value provides the density for a free foam rise, the cutting height and the weight of the cut being indicative of the potential efficiency of use of the foam as it is molded. In subsequent examples, the components of the foam are poured (fill weight, g) into a mold which has parallel channels and the foam being raised is forced to flow into 180 bends as and when that it moves in these channels. The part of the foam that flows past the last channel is cut (weight of the piece, g). This method provides information on moldability, foam utilization efficiency, foam pressure, possible shrinkage problems (closed cell foam) and potential

gas release problems.

  (6) Foams of Examples II-V have a uniform fine-cell structure and an excellent reaction profile. A standard formulation used

2491C7 '

  industrially (see Example X) shows rise times and disappearance of the character

  sticky of 80 and 330, respectively.

EXAMPLES VI - X

  These examples illustrate the use of the crosslinking agent of the invention as an additive for semi-flexible foam promoting a better cell structure and acting as a surfactant and regulator Formulation, parts in poCs VI VII Constituent B

"THANOL SF-3950" 97.5 97.5

Polyol Polyol L-1217 2,5 2,5

"NIAX 50-970 2" 5.8 5.0

  Crosslinking agent A 0.2 0.5 Water 2.2 2.2

"THANCAT DD3" 0,35 0,35

"THANCAT DMDEE4" 0,35 0,35

Carbon black paste 2.0 2.0

cells.

VIII IX X

97.5 2.5, 0 1.0 2.2 0.35 0.35 2.0

0 97.5,

___- 2.5

6.0

6.0 ----

2,5 2,2

0.30 0.35

0.30 0.35

2.0 2.0

Constituent A

"MONDUR MR"

  Cutting test Foam rising time, s Stickyness disappearing time, s Cutting height cm Cutting weight, grams Casting test Filling weight, grams Workpiece weight, grams

51.3 50.4 50.4 46.5 45.5

18.5 18.5 69.3 69.8

310,305

301 288 302

18.5 73.0

302,310

2755 306

  (1) produced by WITCO CHEMICAL CO.

  (2) produced by UNION CARBIDE CO., Agent

crosslinking.

  (3) Ether-2-dimethylaminoethyl-3-dimethyl

  aminopropyl, produced by TEXACO CHEMICAL CO. (4) Ether B, Bdimorpholinodiethyl, product

by TEXACO CHEMICAL CO.

  (5) excellent efficiency (lower foam weight for filling the mold) is noted when directly substituting cross-linking agent A for a typical commercial formulation (Example X). This higher efficiency results from the use of higher water concentrations, which is rendered

  possible by the use of this crosslinking agent.

  It is also noted in these examples that when using the crosslinking agent A, a

better cell structure.

EXAMPLES XI - XV

  These examples illustrate the use of crosslinking agents. These crosslinking agents have a much lower functionality than the crosslinking agent A of the invention and are introduced into the formulation to replace a portion of the crosslinking agent A in order to reduce the overall crosslinking density while conserving

  the required properties of stress resistance.

  A better use efficiency is obtained while the incorporation of the crosslinking agent A provides the improvements mentioned above, the cell structure, the moldability and

other factors.

  Formulation, parts by weight XI XII XIII XIV XV Constituent B

  "THANOL SF-3950" 100.0 100.0 100.0 100.0 100.0

  Cross-linking agent A 6.0 6.0 6.0 6.0 6.0

"THANOL C-150Q1"

"THANOL C-1651"

"THANOL C-2001"

"THANOL TR-380"

Dipropylene glycol Water

"THANCAT DPA"

  Carbon Black Paste Constituent A

"MONDUR MR"

  Cutting test Foam rising time, s Stickyness disappearing time, s Cutting height, cm 2.0 ___

* 2.0 ---

--- 2.0

_ _ _ - - -

2.5 1.2 2.0 2.5 1.2 2.0 2.5 1.2 2.0

, 49.8 49.4

65 63 67

17.8 18.5 18.5

Weight of the cup, grams

69.53 68.5 72.0 74.0 68.43

  (1) carbamate diol crosslinking agents 150: 2-hydroxyethyl-2-hydroxyethyl carbamate, 2-hydroxyethyl-2-hydroxypropyl carbamate,

  : 2-hydroxyethyl-2- (2-hydroxyethoxy) carbamate

  ethyl). U.S. Patent 3,995,814

  describes these products. Produced by TEXACO CHEMICAL CO.

  (2) aminopolyol difunctional crosslinking agent

  This is the product of the aniline reaction and about 6-7 moles of ethylene oxide. See U.S. Patent 4,067,833. Produced by TEXACO

CHEMICAL CO.

  (3) Note the weight of the cut (use efficiency) compared to Examples 3 and 4; the improvement in efficiency results from the incorporation of these crosslinking agents-diluents. We keep

  nevertheless an excellent reaction profile and excellent

slow cell structure.

2 4 9 10 75

  2.0 2.5 1.2 2.0 48.2 2.0 2.5 1.2 2.0, 5 19.1 18.3

EXAMPLES XVI - XXII

  These examples illustrate the use of diluent crosslinking agents in semi-flexible foams for dashboards. In these examples, lower total contents of the crosslinking agent are used, which leads to a softer foam than

described in Examples XI-XV.

  Formulation, Parts by Weight Constituent B

"THANOL SF-3950" 100.0 100

Crosslinking agent A 3.6 3

Dipropylene Glycol 2,4 ---

Propylene glycol ---- 2 Water 2.5 2

"THANCAT DPA" 1.0 1

  2.0 'Carbon Black Paste 2 Constituent A

"MONDUR MR" 48.3 51

  Cross-section test Foam-up time, s 92 82 Stickiness disappearance time, s 270 270 Cut height, cm 18.8 19, Cutting weight, g 68.6 66, Casting test Filling weight , g 307 305 Weight of the piece, g

O 100.0 100.0 100.0

6-3.6 3.0 2.4

_ _ - - - - --__ _ _ _ _

, 0 100.0

2.5 2.0

4 2.4 2.0 1.6 2; 5

2,5 2,5 2,5 2,5

O 1.6 1.6 1.6 1.6

0 2.0 2.0 2.0 2.0

6 51.8 49.9

48.0 51.0

2.0 2.5 1.6 2.0 48.9

63 66 60 64

301 399

180

19.6 19.6

63.6 63.2

19.8 63.6 19.8 61.5, 1 62.1

313 307 306 312 308

308 300 296 294 308

  (1) excellent foam utilization efficiency is obtained when using diluent crosslinking agents, without losing the advantages offered by the crosslinking agent A when

its concentration is reduced.

EXAMPLES XXIII - XXIX

  These examples illustrate the influence of

2491C75 higher water content in the formulations.

  Higher water concentrations give lower density foam, provide better

  efficiency and a lower weight per piece. Con-

  Higher water centrations in a formulation generally result in poorer moldability, and greater voids, but these higher water concentrations are permitted by the presence of Formulation, p parts. Constituent B XXIII X

"THANOL SF-3950" 100.0 1

Retention agent

  culation A 3.0 Propylene glycol 3.0 Water 2.5

"THANCAT DPA" 1,2

  Carbon black paste 2.0 Constituent A

"MONDUR MR"

  Cutting test Foam rising time, s 76

Time of disappearance

characterization

  tacky, s 240 2 Height in cut, cm 19.6 Weight of cut, g 63.7 Casting test

Fill weight

  of the mold, g 318 Weight of the molded part 298, crosslinker A. XXV, 3.0 3.0 2.7 1.2 XXVI, 3.0 3.0 2.8 1, 2 XXVII, 0 3, 0 3.0 2.9 1.2

XXVIII

oo, o 3.0 3.0 3.0 1.2

2.0 2.0 2.0 2.0

68 65 60

240 240 210

, 1 20.1 20.3 21.1

, 9 60.1 59.9 54.8

323 322 324 330

284,286,280,263

XXIX, 0 6.0 3.0 1.2 2.0, 6 58.1

2 4 9 1 0 7 5

  (1) refers to a laboratory mold for evaluation of moldability. In the case of castings using a machine where dashboards are actually molded, these data are not always collected. One of the values (example XXXXII) is excluded to make a comparison with

  the classic system of commerce (example XXX).

  (2) in these machine castings, the material sprayed by the machine into the mold cavity and molded with an inserted structural member and a vinyl skin. The foam is spread by hand in the mold, it is closed and, after a time

  predetermined, is opened, then the part is removed from the mold.

  The weight of the foam is adjusted by playing on the time

spraying machine.

  (3) In these tests, the material was not distributed evenly enough to provide a complete filling and the finished article included

  a small part "filled unsatisfactorily.

  (4) The net weight of the dashboard mold refers to the actual weight of foam introduced

in the mold.

  (5) note the excellent efficiency of u-

  use of the resulting foam while maintaining excellent moldability (absence of voids) compared to the standard (Example XXX). An example of a single machine test is described here (Example XXX) but when a large number of tests are carried out, the number of voids varies from 1 to 5 per mold in the zone.

  defrosting where voids are counted.

  Formulation, Parts by Weight Constituent B

"THANOL SF-3950"

Polyol Polyol L-1217

"NIAX 50-970"

  Propylene glycol Crosslinking Agent Water

"THANCAT DD"

"THANCAT DMDEE"

"THANCAT DPA"

  Carbon black PS Constituent A

"MONDUR MR"

  Cutting test Foam rising time, s Stickyness disappearing time, s Height, cm Weight, g Molding test Filling weight, g Weight of the piece, g

XXX XXXI

97.5 97.5

2,5 2,5

6.0 5.0

---- 0.25

2,2 2,2

0.35 0.35

0.35 0.35

2.0 2.0

XXXII XXXIII

97.5 100O, 0

2.5 -----

, 0 ....

0.25 5.0

2,2 2,5

0.35 ----

0.35 0.3

_- 0.9

2.0 2.0

, 2 49.5 49.5 46.6

XXXIV XXXV XXXVI

, 0 _____

XXXVII XXXVIII

0 100.0 100.0

_____ -----___

, 0 _ _ _

, 0 6.0 3.6 3.6 2.4

---- 2,4 2,4 3,6

2.5 2.5 2.5 2.5 2.5

  _ _ _ _ - - - - - - - - - - - - - - - - -

0.3 0.9 2.0

0.75 1.0

2.0 2.0

46.6 47.6 52.8

74 72 ---- 55 ---- 54

17.5 17.8

___- 195

----. 19.1

---- 240

---- 17,8

1.0 2.0 52.8 1.0 2.0, 3

---- 54

19.3

---- 240

---- 19.8

  LA, Nr Cu /. (Continued) Dashboards molding test Empty Weight (kg) Operating conditions of the machine Casting time, s Temperature, OC B A Mold

  XXX XXI XXII XXXIII XXXIV XXXV XXXVI XXXVII XXXVIII

two none none

1,362 1,380 1308

none none none

1,407 1,4407 1,362

7.8 7.8 7.8 7.8 7.8 7.8

none none none

1,208 1,426 1,208

6.0 7.8 7.0

27 26 26 30 27 d 35 34 33 33

24 25 25 27 26 27 29 27 27

32 32 32 29 29 29 29 29 32

  Ln% r- o% 4r Cu O Formulation, parts by weight Constituent B

"THANOL SF-3950"

Polyol Polyol L-1217

"NIAX 50-970"

  Propylene glycol Crosslinking Agent Water

"THANCAT DD"

"THANCAT DMDEE"

"THANCAT DPA"

  <4 Carbon black paste Constituent A

"MONDUR MR"

  Cutting test Foam rising time, s Stickyness disappearing time, s Height, cm Weight, g Molding test Filling weight, g Weight of the piece, g

  XXXIX XXXX XXXXI XXXXII XXXXIII XXXXIV XXXXV XXXXVI

  1Q0.0 lQOO 2.4 3.6 2.5 _____ 1.0 2.0, Q _____ _3.0 3.0 3.0 2.5 1.0 2.0, 0 _____ 3.0 3.0 2.5 _____ 1.0 2.0, 0 3.0 3.0 2.5 ----- 1.0 2.0

, 3 54.0 54.0 53.6

57 - - 49

____ 19.3

____ 65

_ _ _ _ _ - - - - - - - - - -

_____ - - - - --- -

  , 1, 0 2.0 3.0 2.5 ----- 1.0 2.0 54.6 Q, 0 2.0 3.0 2.5 _____ 1.0 2.0, 0 _____ 2 , 0 3.0 2.5 _____ 1.0 2.0, 0 _____ _____ 2.0 3.0 2.5

--------

--------

1.0 2.0

54.6 54.6 54.6

- - - - - -

255 .... ---- -_

19.8 ....

63. ... -----

/. r- C% I

----- -----

----- ----- -----

  a "N% - O (Continued) Empty Dashboard Molding Test Weight (kg)

Operating conditions-

  of the machine Casting time, s Temperature, C B A Mold none

1,244 1,244

7.0 7.0

33 33

27 28

32 27

  none 1,199 7.2 none 1,262 7.2 none 1,162 6.8 none none

1,208 1,253

7.0 7.0

249 1075

Claims (9)

  Process for the production of a molded flexible polyurethane product, characterized in that a polyol, a polyisocyanate, water and a crosslinking agent, which consists of ethylene oxide adduct of a product of Mannich condensation prepared by reaction of nonyl phenol, diethanolamine and formaldehyde.   2. The process according to claim 1, wherein   characterized in that the crosslinking agent has a hydroxyl value in the range of about 230 to about 500.   3. Process according to any one of the   Claims 1 and 2, characterized in that the polyol is an alkylene oxide adduct of an initiator containing both diol constituents and triols.   4. Process according to any one of the   in which the polyol comprises at least 80% of primary hydroxyl end groups and in that it has an equivalent weight from about 1,600 to 2,000.   5. Process according to any one of the   prior art, characterized in that the polyol is a mixture of propylene oxide end products obtained by addition to propylene oxide,   propylene glycol and glycerol.   6. Process according to any one of the   previous indications, characterized in that the poly-   organic isocyanate is manufactured by phosgenation   of the product of the reaction of aniline and   dehyde having a functionality of 2.2 or more.   7. Process according to any one of the   previous indications, characterized in that 2491C75   catalyst consisting of the two-mole propylene oxide dimethylaminopropylamine adduct is present   8. Process according to any one of the   preceding statements, characterized in that water is present in the reaction mixture in a proportion of 2.2 to 4.5 parts by weight per 100 polyol parts.   9. Process according to any one of the   previous diications, characterized in that a diol   low molecular weight is also present.