Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Cellular products or processes of preparing a cellular...
Reexamination Certificate
1999-11-17
2001-05-22
Cooney, Jr., John M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Cellular products or processes of preparing a cellular...
C521S131000, C521S137000, C521S155000, C521S159000, C521S170000, C521S174000
Reexamination Certificate
active
06235799
ABSTRACT:
The invention provides a process for preparing flexible to semi-rigid polyurethane materials with compacted edge zones with a given degree of hardness and a much more flexible cellular core, so-called integral foams, in which physical blowing agents from the set of C
6
hydrocarbons are used.
Until its ozone-damaging properties were recognised monochlorotrifluoromethane (R11) was almost exclusively used as a blowing agent for building up flexible to semi-rigid polyurethane moulded items with compacted edge zones and a cellular internal structure. Accompanying this finding a number of new fluorine-containing blowing gases of the hydrochlorofluorocarbons (HCFC) and hydrofluorocarbon (HFC) type were developed and tested. Initially, hydrocarbons were also used in these tests, as can be seen from a number of patents (DE-A 3 430 285, U.S. Pat. No. 3,178,490, U.S. 3,182,104, U.S. 4,065,410, DE-A 2,622,951, U.S. Pat. No. 3,931,106 and DE-A 2 544 560).
Since disclosure of the ozone-damaging behaviour of hydrofluorocarbons, there has been no lack of attempts to use other types of blowing agents to prepare cellular polyurethanes. Thus in EP-A 364 854, a process for preparing moulded items with a compacted edge zone and a cellular core, preferably soles for shoes, from starting materials known per se is described, but using low boiling aliphatic and/or cycloaliphatic hydrocarbons with 4 to 8 carbon atoms in the molecule. The following are mentioned, inter alia, as aliphatic or cycloaliphatic hydrocarbons: cyclobutane, cyclopentane cycloheptane, cyclooctane, butane, n- and i-pentane, n-and i-hexane, n- and i-heptane and n- and i-octane, preferably cyclohexane and i- and n-pentane.
The object of the invention was to develop a flexible integral foam with a recognisable integral structure which is identical to or similar to products blown using HFCs and HCFCs.
Surprisingly, it has now been found that integral foams can be obtained by using specific C
6
hydrocarbon mixtures as blowing agents, these having impact strengths and surface hardnesses which are similar to those of systems blown with R11 and R141b and which are much better than systems blown with n-pentane, cyclopentane, R22 or R134a.
The invention therefore provides a process for preparing flexible to semi-rigid polyurethane moulded items with a compacted edge zone and a flexible cellular core, which is characterised in that
a) organic and/or modified organic polyisocyanates and/or polyisocyanate pre-polymers are reacted with
b) at least one polyol component with an OH-value of 20 to 200 and a functionality of 2 to 6, preferably 2 to 3,
c) optionally combined with a polyol component with an OH-value of 201 to 899 and a functionality of 2 to 3 and with
d) at least one chain-lengthening component with an OH- or amine-value of 600 to 1850 and a functionality of 2 to 4 and with
e) optional additives, activators and/or stabilisers known per se
in the presence of water and in the presence of C
6
hydrocarbon mixtures including 2-methylpentane, 3-methylpentane, 2,3-dimethybutane and 2,2-dimethylbutane, with a boiling range of 55 to 65° C.
In the process according to the invention, it is important that the boiling point range of the C
6
hydrocarbon mixture is within the stated range, preferably within the range 58 to 63° C.
Obviously it is also possible to use C
6
hydrocarbons in the mixture which have a boiling point outside this range. The only critical factor is that the proportion of these C
6
hydrocarbons is chosen in such a way that the stated boiling range is obtained for the mixture. A C
6
hydrocarbon mixture consisting of 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane and 2,2-dimethylbutane, wherein the amounts of hexanes used are within the following ranges: 45 to 65 wt. % of 2-methyl pentane, 15 to 30 wt. % of 3-methylpentane, 10 to 25 wt. % of 2,3-dimethylbutane and 0 to 10 wt. % of 2,2-dimethylbutane, the percentages adding up to 100 wt. %, is particularly suitable for a C
6
hydrocarbon mixture for the process according to the invention.
As mentioned previously, water may also be used as a blowing agent in the process according to the invention. The amount of water which is also included in polyurethane formulations is generally 0.05 to 0.6 parts by weight, preferably 0.1 to 0.4 parts by weight, with reference to 100 parts by weight of components b) and c) (polyol components). The amount of C
6
hydrocarbon mixture is 0.2 to 10 parts by weight, preferably 0.5 to 8 parts by weight, with reference to 100 parts by weight of components b), c), d) and e) or b) and d) or b), c) and d) or b), d) and e), depending on the particular composition of the reaction products.
The flexible to semi-rigid polyurethane foams with integral structures prepared according to the invention possess Shore A hardnesses between 60 and 90 in the edge zone and compressive strengths between 80 and 300 kPa at densities between 400 and 600 kg/m
3
.
The combination of high surface hardness (given as Shore A) and low compressive strength of the moulded items is of particular advantage in the process according to the invention as it indicates a recognisable integral structure.
This combination of properties is only obtained with the C
6
hydrocarbon mixtures according to the invention and with the halogenated hydrofluorocarbons R11 or R141b which can no longer be used for environmental reasons.
Suitable organic polyisocyanates (a) are aliphatic, cycloaliphatic, araliphatic and, preferably, aromatic polyfunctional isocyanates known per se, such as are mentioned for example in EP-A 364 854. Toluylene diisocyanates and the diphenylmethane diisocyanates, their modified products or the corresponding pre-polymers which may be modified by urethane, urea, biuret, allophanate, carbodiimide or uretdione groups are particularly suitable. Particular aromatic polyisocyanates which may be mentioned are 4,4-diphenymethane diisocyanate, mixtures of 2,4′- and/or 4,4′-diphenylmethane diisocyanate or crude MDI products and/or 2,4- and/or 2,6-toluylene diisocyanate and their mixtures.
Compounds which are suitable as polyol component (b) are those with an OH-value of preferably 20 to 200, in particular 20 to 50 and a functionality of preferably 2 to 3, wherein polyetherpolyols have a molecular weight of 2000 to 8000 and polyesterpolyols have a molecular weight of 2000 to 4000. Polyols with OH-value of 201 to 899 and a functionality of 2 to 3 may optionally also be used as polyol component (c). Particularly suitable polyols have proven to be compounds selected from the group of polyetherpolyols and polyesterpolyols, such as are obtained by the addition of alkylene oxides such as ethylene oxide and propylene oxide to polyfunctional starters such as ethylene glycol, propylene glycol, glycerine, trimethylolpropane, sorbitol and/or ethylenediamine or by condensation of dicarboxylic acids such as adipic acid, succinic acid, glutaric acid, suberic acid, sebacic acid, maleic acid, phthalic acid with mainly bifunctional hydroxy components such as ethylene glycol, propylene glycol built up from ethylene oxide and propylene oxide as well as glycerine, trimethylolpropane, ethylenediamine, propylene glycol, ethylene glycol, sorbitol and their mixtures as starters. Modified polyols such as those obtained by grafting polyols with styrene and/or acrylonitrile, as polyurea dispersions or as PIPA polyols, may also be used as polyol component (b).
Polyetherpolyols and polyesterpolyols may be used either individually or mixed with each other.
Compounds suitable for use as component (d) are in particular those with an OH- or amine-value of 600 to 1850 and a functionality between 2 and 4, in particular 2 and 3.
The following may be mentioned by way of example here: glycols such as ethylene glycol, 1,4-butanediol, glycerine, trimethylolpropane and their short chain alkoxylation-products as well as diethyltoluylene diamine isomers. The cross-linking component (chain-lengthening component) d) is used in amounts of 3 to 20 wt. %, with reference to the polyol component b) and c) (if pres
Avar Geza
Eisen Norbert
Haas Peter
Bayer Aktiengesellschaft
Brown N. Denise
Cooney Jr. John M.
Gil Joseph C.
LandOfFree
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