Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-04-06
2001-11-06
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S282000, C526S075000, C526S204000, C526S272000, C560S220000
Reexamination Certificate
active
06313250
ABSTRACT:
The present invention relates to polyfunctionally reactive polymeric substances containing structural units of dihydrodicyclopentadiene and/or its oligomers.
Numerous patents relate to unsaturated polyester resins containing structural units derived from dicyclopentadiene (═DCPD) or dihydrodicyclopentadiene (═DHCPD), which are generally used dissolved in monomeric reactive diluents such as styrene, &agr;-methyl-styrene, vinyltoluene, allyl phthalate, acrylates, vinylates, vinyl ethers or the like.
Known monomeric compounds are for example maleic acid dihydrodicyclopentadienol monoester (CAS 56 102-16-0, 27 063-31-6, 28 347-17-3, 25 102-16-0, 27 063-31-6, 28 347-17-3, 29 725-36-8, 53 702-55-9, 56 102-16-0, 74 033-90-2, 100 429-54-7),
maleic acid dihydrodicyclopentadienol diester (CAS 116 296-55-0, 151 379-31-6, 114 422-30-9),
ester of maleic acid dihydrodicyclopentadienol monoester with n-butanol (CAS 117 205-58-0, 116 057-35-3),
ethylhexanol (CAS 17 205-57-9, 116 057-34-2),
isopropylene glycol (diester) (CAS 78 099-70-4),
ethylene glycol (mono- and diester) (CAS 78 099-70-4, 78 820-56-1),
trimethylolpropane (monoester) (CAS 98 312-78-8),
propylene glycol (monoester) (CAS 98 520-75-3),
1,3-butanediol (monoester) (CAS 98 392-84-8),
diethylene glycol (mono- and diester) (CAS 73 794-24-8),
neopentylglycol (monoester) (CAS 121 830-76-0).
It is an object of the present invention to provide novel polyfunctionally reactive polymeric substances which have significant advantages over the prior art in respect of preparation, processing and application spectrum.
We have found that, surprisingly, this object is achieved by polyfunctionally reactive polymeric substances containing dihydrodicyclopentadiene or its oligomers bonded to certain polymer backbones via certain bridging members.
The present invention accordingly provides polyfunctionally reactive polymeric substances which contain at least two structural units of the general formulae (I) and/or (II)
in the molecule and whose polymer backbone linkages are C—C bonds, ether bonds, urethane bonds, amide bonds, ketone bonds or combinations thereof.
In these novel polyfunctionally reactive polymeric substances, the structural units of the of the general formulae (I) and/or (II) are bonded to the polymer backbone via bridging members —X— conforming to the formulae (III) and/or (IV)
where —X— is oxygen,
In the polymeric substances of this invention, the structural units of the general formulae (I) and/or (II) can be incorporated as reaction products of compounds of the formulae (V) and/or (VI)
with polymeric substances which carry groups which are reactive toward hydroxyl groups, such polymeric substances being obtainable for example as reaction products of compounds of the formula (V) and/or (VI) with polymers having carboxyl groups, isocyanate groups, epoxide groups or hydroxyl groups.
In a particularly preferred embodiment of the polymeric substances of this invention, the structural units of the general formulae (I) and/or (II) are incorporated as reaction products of compounds of the formulae (VII) and/or (VIII)
with polymeric substances which carry groups which are reactive toward carboxyl groups, such polymeric substances being obtainable for example as reaction products of compounds of the formulae (VII) and/or (VIII) with polymers having isocyanate, epoxide, hydroxyl and/or amino groups as groups which are reactive toward carboxyl groups.
The polyfunctionally reactive polymeric substances of this invention generally have average molecular weights M
n
within the range from 200 to 1000000, preferably within the range from 500 to 50000.
The polymeric substances of this invention carry structural units of the general formulae (1) and (II) derived from dihydrodicyclopentadiene (DCPD). They may be linear or else singly or multiply branched and they have schematically the structures which are represented in the formulae (IX) and (X), but which can also have branching forms other than those shown in the below-shown examples, where —X— is a bridging group, and D— is a structure of the formulae (I) and/or (II).
Substances are readily available in which —X— is an ester group and which are obtained by addition of DCPD onto polyfunctional polycarboxylic acids. This reaction can be carried out with advantage in the presence of catalysts, for example boron trifluoride etherate.
Very ready availability is an attribute of the formula (VII) or (VIII) adducts of maleic anhydride and water with DCPD, whereby the substances of this invention are obtainable by reaction with carboxyl-reactive substances. Such carboxyl-reactive substances include for example mono- and polyfunctional polymeric hydroxyl compounds, carboxylic esters of mono- and polyfunctional, monomeric or polymeric hydroxyl compounds, mono- and polyfunctional, monomeric or polymeric epoxides, hydroxy-functional natural oils and resins, epoxidized natural oils and resins, mono- and polyfunctional, monomeric or polymeric isocyanates and also mono- and polyfunctional monomeric or polymeric amines.
Similarly, dihydrodicyclopentadienol of the formula (V) is commercially available and can be obtained for constructing the substances of this invention, by reaction with substances which are reactive with OH groups.
Such hydroxyl-reactive substances include for example polyfunctional monomeric or polymeric carboxyl compounds, polyfunctional monomeric or polymeric epoxides, carboxyl-functional natural oils and resins, epoxidized natural oils and resins, polyfunctional monomeric or polymeric isocyanates, polyfunctional monomeric or polymeric hydroxyl compounds, polyfunctional, monomeric or polymeric carboxylic esters.
When the substances of this invention contain ethylenic double bonds, for example as maleic or fumaric esters, grafting with cyclopentadiene produces endomethylenetetrahydrophthalic acid structures of the following formula:
All the routes mentioned to the substances of this invention are exemplary methods of preparation, which are usually also advantageous. However, the invention is directed not just to substances obtained by the outlined methods.
An important class of claimed substances for the present invention are the esters of substances of the formulae (VII) and (VIII) with branched alkane-, alkene- and alkyne-diols, ethoxylated or propoxylated trimethylolpropane, pentaerythritol, ethoxylated or propoxylated pentaerythritol, glycerol, ethoxylated or propoxylated glycerol, neopentylglycol, ethoxylated or propoxylated neopentylglycol, 2-ethyl-2-butyl-1,3-propanediol, ethoxylated or propoxylated 2-ethyl-2-butyl-1,3-propanediol, with sorbitol, inositol, anhydrosorbitol and the alkoxylation products of these substances, the esters of inner ethers of polyols such as, for example, ditrimethylolpropane, dipentaerythritol, the esters of ethoxylated or propoxylated inner ethers of polyols such as, for example, ditrimethylolpropane or dipentaerythritol, dimethylolpropionic acid, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ethers, polyethylene glycol monoalkyl esters, polypropylene glycol monoalkyl esters, polyester- and polyether-polyols of the type polyethylene oxide, polypropylene oxide, polytetrahydrofuran and polycaprolactone.
The nature of the alkoxylating agent and the degree of alkoxylation also make possible to control properties of the end products such as, for example, hardness, hydrophilicity and elasticity. Such polyfunctional hydroxyl compounds may also be only partially esterified with substances of the formulae (VII) and (VIII), in which case the remaining hydroxyl groups can either remain free or be esterified or etherified with other substances or reacted with other, reactive substances, for example isocyanates or epoxides. Suitable for this purpose are polyols which are only partially esterified with substances according to the formulae (VII) and (VIII), while the other hydroxyl groups can be reacted with substances which carry ethylenic double bonds. Such substances then carry on the same molecule not only the esters of the substan
Blum Rainer
Haeussling Lukas
Reich Wolfgang
BASF Aktiengesellshaft
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Wu David W.
Zalukaeva Tanya
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