Internal release agents for producing polyurethane moulded...

Details Internal release agents for producing polyurethane moulded... Internal release agents for producing polyurethane moulded...

2000-03-22

2002-10-29

Niland, Patrick D. (Department: 1714)

Plastic and nonmetallic article shaping or treating: processes

Mechanical shaping or molding to form or reform shaped article

Shaping against forming surface

C524S127000, C524S157000, C524S284000, C524S589000, C524S590000

Reexamination Certificate

active

06471905

ABSTRACT:

The present invention relates to improved internal mould release agents for producing cellular or compact polyurethane mouldings, in particular polyurethane mouldings which are laminated or coated with other materials.
Internal mould release agents for producing polyurethane mouldings, in particular polyurethane foams, have long been known. Thus, for example, mould release agents are described in DE-A 21 21 670, 19 53 637 and 23 07 589 in relation to the production of foams, which mould release agents consist of salts of aliphatic carboxylic acids with preferably primary amines or amide or ester group-containing amines, the total carbon value of which is at least 25 carbon atoms.
U.S. Pat. No. 4,024,088 mentions, inter alia, organophosphorus compounds as internal mould release agents Which contain at least 8 carbon atoms per molecule. Furthermore, internal mould release agents are known from U.S. Pat. No. 4,098,731 which are based on metal salts of a carboxylic acid, amidocarboxylic acid, phosphoric acid or boric acid in combination with specific tertiary amines. U.S. Pat. No. 4,098,731 also describes internal mould release agents used in the production of polyurethane mouldings and based on salts of carboxylic acids having at least 8 carbon atoms and tertiary amines. Moreover, internal mould release agents are known from U.S. Pat. No. 4,220,727 which consist, inter alia, of metal salts of fatty acids and specific quaternary aralkyl ammonium salts. Zinc carboxylates with long-chain carboxyl residues (8 to 24 carbon atoms) are known as internal mould release agents, for example from U.S. Pat. No. 4,519,965, U.S. Pat. No. 4,581,386 and U.S. Pat. No. 4,111,861. In addition, the use of higher fatty acid esters as mould release agents is known from U.S. Pat. No. 4,130,698.
The mould release agents known hitherto exhibit a wide variety of disadvantages from the point of view of the production of cellular or compact polyurethane mouldings. Thus, the metal salts of higher carboxylic acids tend, after a time, towards crystallisation and gel formation, if they are added to the starting components for producing polyurethane mouldings, whereby the viscosity and flow behaviour of the polyurethane compositions are disadvantageously modified. With other mould release agents, in particular those with non-polar or polar constituents, a two-phase system forms owing to the frequently inadequate solubility of the components in the polyurethane starting materials, which leads to problems processing the polyurethane moulding compositions.
Another considerable disadvantage of the internal mould release agents known hitherto is the so-called build-up in the mould, whereby the mould contours gradually become clogged over relatively long cycles. The fine contours of the moulds used, which are stuck up and clogged with polyurethane compositions, may be returned to the original state only by subsequent complex cleaning, which naturally causes an interruption in production.
The object of the present invention is to provide internal mould release agents which avoid the above-described disadvantages of previous mould release agents and therefore have altogether an improved range of properties.
The present invention therefore relates to improved internal mould release agents for producing polyurethane mouldings consisting of
a) ammonium or metal salts of phosphoric acid esters of the formula (I)
 wherein
R stands for C
1
-C
10
, preferably C
4
-C
8
alkyl,
X denotes OR
1
, with R
1
being equal to R or O—Y
+
and
Y stands for NH
4
and N(R
2
,R
3
,R
4
,R
5
), wherein R
2
to R
5
are the same or different and denote hydrogen of C
1
-C
10
alkyl, wherein the C
1
-C
10
alkyl residue may be mono- or polysubstituted by OR
6
or NR
6
R
7
and R
6
and R
7
have the meaning of hydrogen or C
1
-C
10
alkyl,
or wherein R
2
to R
5
signify
 in which
R
8
and R
9
are the same or different and stand for C
1
-C
10
alkyl or hydrogen,
m is a whole number from 2 to 4 and
n is a whole number from 1 to 5,
or
Y stands for metals of the first main group of the periodic system of elements (Mendeléeff),
b) ammonium salts of carboxylic acids of the formula (II)
R
10
COO
−
Z
+
  (II),
in which
R
10
stands for hydrogen, C
1
-C
9
alkyl or C
6
-C
10
aryl, which may optionally be substituted by C
1
-C
3
alkyl groups, and
Z has the meaning of Y with the exception of the above-mentioned metals of the first main group of the periodic system of elements,
and/or
c) ammonium or metal salts of sulfonic acids of the formula (III)
 in which
R
11
has the meaning of R
10
and Y has the meaning given in formula (I).
Particular mention is made of the following as C
1
-C
10
alkyl residues of the above-mentioned formulae:
n-butyl, iso-butyl, n- and iso-pentyl, 2-ethylhexyl, octyl, n-propyl, iso-propyl, ethyl, methyl, nonyl, decyl, in particular n- and iso-butyl, n- and iso-pentyl, 2-ethylhexyl, octyl.
The residue Y of the above-mentioned formula stands, particularly preferably, for NH
4
⊕
, N(CH
3
)
3
H
⊕
, N(C
2
H
5
)
3
H
⊕
, N(C
2
H
5
)
4
⊕
, HO—CH
2
CH
2
—N(CH
3
)
2
H
⊕
, NH
2
(CH
2
)
3
N(CH
3
)
2
H
⊕
, (CH
3
)
2
N—(CH
2
)
3
—N(CH
3
)
2
)H
⊕
,
 CH
3
O—(CH
2
)
2
—N(CH
3
)
2
H
⊕
, HO—CH
2
—CH
2
—NH
3
⊕
, (HO—CH
2
—CH
2
)
2
NCH
3
H
⊕
,
The letter m preferably stands for a whole number from 2 to 3 and n preferably stands for 1 to 3.
The following are worthy of particular mention as metals of the first main group of the periodic system of elements: lithium, sodium, potassium.
The following salts are particularly suitable as mould release agents for producing polyurethane mouldings:
 HOCH
2
—CH
2
NH
3
+
(C
4
H
9
O)
2
P(O)O
−
NH
2
—(CH
2
)
3
N(CH
3
)
2
H
+
(C
4
H
9
O)
2
P(O)O
−
⊕
NH
3
—(CH
2
)
3
—N(CH
3
)
2
H
+
2(C
4
H
9
O)
2
P(O)O
−
HO—CH
2
—CH
2
—NH
3
+
(C
8
H
17
O)
2
P(O)O
−
 HO—CH
2
—CH
2
—N(CH
3
)
2
H
+
(C
8
H
17
O)
2
P(O)O
−
NH
2
—(CH
2
)
3
N(CH
3
)
2
H
+
(C
8
H
17
O)
2
P(O)O
−
 HO—CH
2
—CH
2
—N(CH
3
)
2
H
+
C
7
H
15
—COO
−
HO—CH
2
—CH
2
—N(CH
3
)
2
H
+
C
6
H
13
—COO
−
HO—CH
2
—CH
2
—N(CH
3
)
2
H
+
CH
3
SO
3
−
 Na
+
(C
4
H
9
O)
2
P(O)O
−
The following salts are most particularly preferred:
As mentioned, the mould release agents according to the invention are suitable for producing cellular or compact polyurethane mouldings.
The polyurethane mouldings may be produced in conventional manner by reacting
a) polyisocyanates or polyisocyanate prepolymers with
b) at least one compound comprising at least two isocyanate-reactive groups and having a molecular weight of from 400 to 10,000, optionally in the presence of chain extenders of molecular weights ranging from 32 to 399, wherein the reaction of components a) and b) may be performed optionally in the presence of water and/or organic blowing agents, stabilisers, activators together with other auxiliary substances and additives known per se.
In addition to the above-mentioned additives, organic and inorganic fillers may also be added during processing to the polyurethane compositions obtained to reinforce the mouldings. Examples of such fillers are glass fibres, wollastonite, sisal, flax, jute, hemp and/or wood chips.
The principal substances used as stabilisers are polyether siloxanes. These compounds generally comprise a short-chain copolymer of ethylene oxide and propylene oxide combined with a polydimethyl siloxane residue. Such foam stabilisers are described, for example, in U.S. Pat. Nos. 2,834,748, 2,917,480 and 3,629,308.
Examples of catalysts are: tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N′,N′-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues (DE-A 2 624 527 and 2 624 528), 1,4-diazabicyclo-(2,2,2)-octane, N-methyl-N′-dimethylaminoethylpiperazine, bis-(dimethylaminoalkyl)piperazine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine,

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