DE1300690B - Process for the production of a polyurethane - Google Patents

Description

Found a polyol, and for various reasons, an active hydrogen-containing reason is not yet sufficient, the polybonding with formaldehyde and a primary or urethane foam that has been produced to date.
So is z. B. the resistance of polyurethane hard

foam against high temperature and high humidity ih ihd F i f i über

secondary amine to a substituted aminomethyl derivative of the active hydrogen containing Raw material implemented. The procedure for

activity not sufficient. Furthermore, it is often necessary to produce more than 15 of the nitrogen-containing polyols a self-extinguishing or practically non-combustible British patent 1 002 272 can be found in detail To have foam. To do this, you need fire letters.

inhibitors, e.g. B. organic phosphorus compounds, you can make a polyurethane foam from a

can be added. For flame retardant finishing, polyol components are to be produced that exclusively contain or usually as much added compounds require about only 30 to 100 percent by weight thereof and as lent that the properties of the finished polyurethane residue contains a conventional polyol, the normal foam be worsened. is used for the production of rigid urethane foams.

Many of these polyols are well known, e.g. B. in addition, the relative speeds of the and those caused by the reaction of an alkylene divide Responses coordinated with one another generate 25 oxyds. like ethylene oxide, propylene oxide, 1,2-butylene ends, what can be achieved by carefully selecting a cata- oxide, styrene oxide, epichlorohydrin, glycine or gelator system achieved. Usually the catalyst consists of mixing with a polyhydroxy compound, Sator from a tertiary amine, which alone or with z. B. a carbohydrate or an aliphatic mixed with organic tin compounds or aromatic compound (with 3 to 8 hydroxyls. These tertiary amines give the finished 30 groups), such as hexantrio !, pentaerythritol, sorbitol, Foam has an unpleasant amine odor. Methyl glucoside. Sucrose, 1,3,3-tris- (hydroxyprop-

Many of the disadvantages described can be obtained by oxyphenol) propane, etc., the use of new, nitrogen-containing poly- In addition, alkylene oxide adducts can be certain oils are switched off, their catalytic we amines, ζ. B, propylene oxide adducts of ethylene steering is so large that diamine or aminoethylpiperazine are used to produce hard 35, Foams do not require an additional catalyst, as do certain hydroxyl-terminated polyesters is. Surprisingly, you can do it with the pen. those from dibasic acids such as phthalene according to the invention used polyols produced acid and adipic acid, and diols or triols, Polyurethane foams flame retardant and dimensionally accurate z. B. make diethylene glycol, glycerin or trimethylol, if special fire retardants have been added 40 propane has been manufactured, will. In addition, the new foams are free from For the production of foams according to the invention

Amine odor, which is common in urethane foams. proceed as usual, only without a catalyst.

The process according to the invention for the production of polyisocyanates, blowing agents, foam stabilizers of a polyurethane by implementing an organ and flame retardant agent, which can be used in the hernia Polyisocyanate with a 'nitrogen-containing 45 position of rigid polyurethane foams as useful Polyol having a hydroxyl number of about 350 to 900 has been shown to be well known and are

z. B. von Frisch and coworkers in »Advances in Technology and Uses of Rigid Urethane Foams (Modem Plastics, 40, 165 [October 1962]) from 1 to 3 50 ben disubstituted on nitrogen.

Aminomethyl groups are present, which are attached to an aroma- In the semiprepolymer process, the semi-

prepolymers by reacting a large molar excess of a polyisocyanate with a polyol manufactured. This Serniprepolymer is then with

or glycide, with at least one of the other polyol and other foam ingredients Nitrogen from these aminomethyl groups are further reacted in the one-step process Substituents 1 to 2 primary and secondary Hy- all foam components mixed at the same time, contains hydroxyl groups. In the semi-prepolymer method of manufacture

The polyol used according to the invention is made of rigid urethane foams according to the invention by adding an alkylene oxide to a Mannich- ^6o , the semi-prepolymer is preferably by condensation product of a phenol compound, setting a conventional polyol of the described-formaldehyde and an alkanolamine at about 30 benen type with such Amount of polyisocyanate up to 200 ⁰ C obtained. These polyols have made hydroxyl, that about 20 to 40 weight percent free numbers of about 350 to 900, preferably 450 to isocyanate groups (relative to the used Ge-600, and a nitrogen content of about 1 to 15 overall ⁶ 5 total quantity of polyisocyanate) in the semi-prepolymer weight percent, preferably 4 to 8 weight percent. are present. A sufficient amount of the polyol The nitrogen is in the molecule as tertiary nitrogen (an OH group / NCO group) is then converted into the semiprepolymer disubstituted in the form of 1 to 3 on the nitrogen in the presence of a foam

characterized in that a polyol with a nitrogen content of about 1 to 15 percent by weight, its nitrogen as tertiary nitrogen in

table core are bound, on which there is also at least one hydroxyalkoxy group, which is composed of ethylene oxide, Propylene oxide, 1,2-butylene oxide, styrene oxide

Stabilizer, a propellant and, in some cases, a fire retardant added.

The most commonly used foam stabilizers are silicone oils, usually silicone glycol copolymers, e.g. B. those of General Electric Company, Dow Corning Corporation, and Union Carbide Corporation. For the Propellants suitable for making urethane foams are disclosed in U.S. Patent 3,072,582 described. Propellants are mostly volatile liquids, e.g. B. trichlorofluoromethane. The fire retardant Agents can be added mechanically or chemically bound in the polymer chain. Mechanically Admixed agents are tris (chloroethyl) phosphate, tris (2,3 - dibromopropyl) phosphate, diammonium phosphate as well as antimony oxide. Chemically bound fire retardants include 1,4,5,6,7, 7 - hexachloro - [2,2,1] - 5 - heptene - 2,3 - dicarboxylic acid (chlorendic acid) and various phosphoric acids Polyols.

While normally an amine catalyst, such as triethylenediamine, triethylamine or dimethylpiperazine, is necessary for a usable polyurethane foam, no amine catalyst is used according to the invention needed. If, on the other hand, you want an acceleration of the driving reaction or a shortening of the Time to tack-free, one of the amine catalysts described can be added.

Suitable organic aromatic or aliphatic polyisocyanates are, for. B. 3,3'-dichloro-4,4'-biphenyl diisocyanate, Diphenyl diisocyanate, ethylene diisocyanate, propylene 1,2-diisocyanate, 1,4-tetramethylene diisocyanate, ρ - phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, 0,0'-, o, p'- and p, p'-diphenylmethane - diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate and mixtures from it.

The examples explain the production of rigid polyurethane foams from the polyols obtained according to the abovementioned patent specification by the semi-prepolymer process.

B e'i s ρ i e 1 1

Rigid polyurethane foams were developed from the nacl. Example 1 of said patent obtained Mannich polyol prepared with the preparations given in Table I. The semi-polymer used contained 27.6% free isocyanate groups and was made from tolylene diisocyanate and a propyleneoxy adduct made of sorbitol (average molecular weight about 700). All components of the preparations with the exception of the semi-prepolymer were premixed and weighed into an aluminum syringe. The semi-prepolymer was weighed into a wax-lined beaker. The polyether component was then quickly injected into the prepolymer and at 4200 rpm for 8 seconds stirred per minute. The foaming mixture was poured into an open mold (15.24 15.24 χ 30.48 cm) poured and allowed to rise. The foams were then 2 hours at 70 ° C in one Maintained oven and allowed to stand at room temperature for 72 hours prior to testing. The properties of the foams are listed in Table I.

Table I.

Preparations, parts by weight

'Semi-prepolymer

Polyol according to example 1

Propellant

Foam stabilizer

Fire retardant additive

NCO / OH ratio

Properties of the foam

Rahmzeit, see

Rise time, see

Density, g / cm ³

Heat distortion temperature ^{, 0 C}

Compressive strength, kp / cm ²

Tensile strength, kp / cm ²

Burn rate, cm / min. ¹ )

K-factor, initial value

Dimensional stability

-18 ⁰ C, dry, 1 week

Volume change in%

Weight change in%

') Burn rate test, ASTM 1692-59 T. *) Self-extinguishing.

200 200 200 140 140 140 55 . 58 60 2.0 2.0 2.0 0 18th 38 1.05 1.05 1.05 25th 25th 25th 105 105 105 0.0299 0.0304 0.032 112 112 104 2.36 2.16 2.23 3.67 3.67 3.70 17th S.E. *) S.E. *) 0.107 0.110 0.114 -0.5 -1.5 -0.7 -1.1 -0.5 -0.7

continuation

82 ° C, dry, 1 week

Volume change in%. .

Weight change in% ......

70 ° C, 100% relative humidity

Volume change in%

Weight change in% ......

+ 6.9
-1.5

+20.3
-6.5

+4.5
-0.2

+ 1.6
-8.3

+ 10.5 -0.6

-1.4 -6.1

15th

² 5

According to the table, all three preparations short cream and rise times were obtained even though no separate catalyst was used. the Foams also showed excellent compressive and tensile strength due to the addition of fire retardants Medium there was no loss of strength. 5% fire retardant (based on all foam components With the exception of the propellant, preparation B produces a self-extinguishing foam, also 10% fire retardant in preparation C.

Example .2

A rigid polyurethane foam was made from the Mannich polyol according to Example 2 of the patent mentioned manufactured. The preparation used and the results obtained are shown in Table II. diisocyanate and a propyleneoxy adduct of sorbitol (molecular weight about 700). Propellant, Foam stabilizer and fire retardant were the same as in Example 1, and the Foaming was carried out similarly to Example 1.

Table II

Weight parts

Semi-prepolymer ...... ', .... 200

Polyol according to Example 2 -.- ... 123

preparation

Propellant 45

Foam stabilizer, 3.0

Fire retardant additive 17.5

properties

Ascent time, see 110

Density, g / cm ³ 0.035

Compressive Strength, kp / cm ² 2.83

Thermal Deformation Point, ⁰ C 132

Burn rate, ASTM 1692-59T not

burning

B e i s ρ i e 1 3

From the Mannich polyol according to Example 2 of the above A number of rigid polyurethane foams were produced in the patent specification. The used Preparations and the results obtained are shown in Table III. Again the same were semi-prepolymers and fire retardants, the same foam stabilizer and blowing agent as in US Pat used earlier examples. The foaming corresponded to that described in Example 1.

Table III

Preparation, parts by weight

Polyol according to example 2 ..

Semi-prepolymer ...

Fire retardant
Foam stabilizer .....
Propellant ...........

properties

Rahmzeit, see

Rise time, see

Time until tack-free,
see ........

Density, g / cm ³

Heat distortion point, ^C C ..........

Compressive strength, kp / cm ²

Tensile strength, kp / cm- ..

1 142 2 3 4th 5 127 6th 224 ' 127 127 152 200 127. 0 200 200 240 17.0 200 2.8 0 17.0 20.5 2.0 36.7 56 2.0 2.0 2.4 53 2.0 10 50 53 64 15th 56 90 16 10 10 85 10 90 70 98 90 85 98 0.0304 70 98 90 0.0314 98 140 0.0322 0.0343 0.0309 130 0.0324 2.84 134 134 130 2.87 134 - 3.09 2.72 2.65 4.42 2.58 4.72 4.47 - 4.32

127 200

36.7 3.0

56

10 103

103 0.0320

4.94

continuation

1 2 3 4th 5 6th 7th Burning rate, mm / sec 3.35 S.E. *) S.E. *) S.E. *) N.B. **) N.B. **) ASTM 1692-59T (4/30 ") Dimensional stability -18 ° C, not humid control -2.4 -1.3 -1.9 -2.2 -0.8 -1.7 - 82 ⁰ C, no damp - control +0.9 +0.9 + 2.0 + 1.1 +0.3 +0.7 - 70 ⁰ C, 100% relative humidity -8.4 + 13.8 + 19.2 + 15; 2 +21.4 + 18.2 - K-factor, initial value at 24 ⁰ C - 0.102 - - 0.104 - -

*) Self-extinguishing.
**) Not burning.

According to Table III, rigid polyurethane foams were made in the absence of a fire retardant obtain; which had better properties than those from the Mannich polyol according to Example 1 of the above Foams produced by the patent. In particular, there was a considerable improvement in the Dimensional stability, thermal flexural strength and compressive strength achieved.

The addition of 5 percent by weight of the fire retardant also did the physical Properties and dimensional stability did not adversely affect, and it became a self-extinguishing foam obtained. Finally, foams were 10 weight percent fire retardant Means in contrast; to those from the polyol according to Example 1 mentioned with a corresponding Amount of fire retardant made foams non-burning. Use like that large amounts of fire retardant was not detrimental to the properties of the finished foam.

Advantageously, it can also be used mostly for the production of rigid urethane foams Semi-prepolymer process, the one-step process can also be used. With the more responsive Isocyanates such as tolylene diisocyanate or hexamethylene diisocyanate should have the catalytic activity of the polyols described by using a mixture of one of these Mannich polyols with one or more of the conventional polyols that are not catalytically active, reduced will. With the less reactive isocyanates, e.g. B. Polymethylene polyphenyl isocyanate and 0,0-diphenylmethane diisocyanate, the polyols according to the invention can be used alone.

As in the prepolymer process, the foams according to the invention are also used in the production of foams Polyols according to the one-step process do not require any special catalysts. The at Propellants, foam stabilizers and fire retardants used are the one step process same as with the semi-prepolymer process. Example 4 shows the use of polyols according to Invention for the production of rigid polyurethane foams in a one-step process.

40

ie i s ρ i el 4

Rigid polyurethane foams were made from the. Mannich polyols produced according to Examples 7 and 8 of the patent mentioned in a one-step process. The preparations used and the results obtained are summarized in Table IV. All ingredients were mixed together and then added to the isocyanate. That finished mixture was 10 seconds at 4200 rpm.

stirred and then poured into an open mold (15.24 15.24 χ 30.48 cm). The foams were cured in an oven ^{at 70 ° C. for 1 hour.}

Table IV

Preparation, parts by weight

Polymethylene polyphenyl isocyanate

Polyol according to Example 7

Polyol according to example 8

Propellant

Foam stabilizer

Fire retardant

214
157

56

214 157

7th
20th

143

100 50

909 53? '37. '

continuation

properties

Rise time

Density, g / cm ³ .......

Compressive strength, kp / cm ²

Tensile strength, kp / cm ² .......

Burn rate, ASTM 1692-59T

83

0.0315
2.81
3.98
not burning

100
0.0349
3.00
4.35
not burning

81

0.0277
0.99
2.49

According to Table IV, rigid polyurethane foams with good properties can be obtained from the Polyols are produced by the one-step process. All preparations resulted in short rise times, foams A and B have excellent dimensional stability. The addition of a fire retardant Means (preparation B) had no adverse effect on the foam properties. Both foams A and B were not burning.

The specified heat deformation point is defined as the temperature at which the compressive strength at 10% compression, measured parallel to the foam rise, 10% of the normal compressive strength amounts to.

Claims (2)

Claims:. 1. Process for the production of a polyurethane by reacting an organic polyisocyanate with a nitrogen-containing polyol having a hydroxyl number of about 350 to 900, thereby characterized in that a polyol with a nitrogen content of about 1 to 15 percent by weight, its nitrogen disubstituted as tertiary nitrogen in the form of 1 to 3 on the nitrogen Aminomethyl groups present, which are bonded to an aromatic nucleus, on which further at least one hydroxyalkoxy group is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, Styrene oxide or glycide is derived, with at least one of the aminomethyl groups on the nitrogen standing substituents 1 to 2 primary and secondary hydroxyl groups is used. 2. The method according to claim 1, characterized in that that the isocyanate is firstly a semi-prepolymer which has about 20 to 40% free isocyanate groups and made from an organic polyisocyanate and a conventional polyol having a hydroxyl number of about 350 to 900 has been used, and this prepolymer with a second nitrogen-containing Polyol as defined in claim 1, is converted.