Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-12-19
2004-12-07
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S064000, C525S312000, C525S099000, C525S118000, C525S127000, C525S128000, C525S437000, C525S447000, C525S451000, C525S455000, C525S458000
Reexamination Certificate
active
06828379
ABSTRACT:
The invention relates to curable resin compositions based on an unsaturated prepolymer, a vinyl ether monomer that can be cross-linked with it and one or more other monomers. An “unsaturated prepolymer” as intended in the context of this application is understood to be an unsaturated polyester, a vinyl ester or a vinyl ester urethane, as are more specifically defined furtheron in this application. The curable resin compositions according to the invention are particularly suitable for use as structural resins. In the context of this application “structural resins” are understood to be resins that are used for the production of moulded parts and other structural elements with a thickness of at least 1 mm. The invention also relates to a method for the preparation of such curable resin compositions, and uses thereof.
Resin compositions based on an unsaturated prepolymer and a monomer that can be cross-linked with it are known from an article by N. Boulkertous in Kunststoffe 84 (1994), 1597-1599. It has been found that the described resin compositions, in which according to the article a vinyl ester resin is cured at a low temperature, cure too slowly, harden insufficiently (i.e. conversion is incomplete) and often also yield a sticky surface. Such problems are also encountered with other types of unsaturated prepolymers. There is however still a great need for structural resins that cure quickly, harden well and/or yield a dry, non-sticky surface. “Quick curing” is in the context of the present application in particular understood to be quick curing at a low temperature, that is, at a temperature of between −20° C. and +110° C., preferably already at ambient temperature, which will usually be between −15° C. and +35° C.
Another disadvantage of the state-of-the-art resin compositions is incidentally often the presence of substantial quantities of styrene as a reactive monomer. In view of the increasingly stringent environmental requirements imposed by legislation on producers and users of resin compositions, there is a great need for the availability of resin compositions with a reduced styrene content. Similar increasingly stringent requirements are also to be found in the field of the use of (meth)acrylates and the like as monomers. In that context aspects of health care in particular (e.g. skin sensitisation) are of importance.
The aim of the invention, now, is to provide curable resin compositions based on an unsaturated prepolymer, a vinyl ether monomer that can be cross-linked with it and one or more other monomers, which do not present the aforementioned disadvantages.
This aim is surprisingly achieved according to the invention because the vinyl ether monomer in the curable resin compositions is a vinyl ether having a general structure according to formula (I) or (II):
A—CH═CH—O—R (I)
or
(A—CH═CH—O)
n
—R′ (II)
where
A represents hydrogen or an alkyl group with 1-3 C atoms, and where, if there is more than one A, the individual A groups may be the same or different
R either represents an aliphatic group, optionally branched, with 1-20 C atoms, which may also contain a cyclohexyl group and in the carbon chain optionally also one or more O and/or S atoms, which group may be substituted with a functional group chosen from either a hydroxyl group or an amino group, optionally substituted with one or two alkyl groups with 1-3 C atoms,
or represents a polyethylene glycol or a polypropylene glycol with an average chain length of between 2 and 10 glycol units, optionally with an aliphatic group with 1-5 C atoms attached to the chain's free hydroxyl group and
R′ either is a residual group that corresponds to an aliphatic group, optionally branched, with 2-20 C atoms, which may also contain a 1,4-dimethylenecyclohexyl group,
or represents a polyethylene glycol or a polypropylene glycol with an average chain length of between 2 and 10 glycol units and
n is 1, 2, 3 or 4, and
the unsaturated prepolymer has an acid number of less than 10 mg of KOH per g, and
where the curing is effected with the aid of a radical-forming system that is unstable in the temperature range from −20° C. to +110° C.
The acid number of the unsaturated prepolymer as intended in this application is the acid number determined according to ISO-2114.
The resin compositions according to the invention are particularly suitable for use as structural resins, they have a short curing time and harden excellently. Thanks to the excellent hardening of the surface, the structural materials obtained with the resin compositions also have a dry surface immediately after production. The vinyl ether monomers moreover differ in a favourable respect from styrene and (meth)acrylates in terms of environmental and health aspects.
It goes without saying that, instead of one vinyl ether monomer according to formula (I) or (II), it is also possible to use mixtures of vinyl ether monomers according to formula (I) and/or (II), and the curable resin compositions obtained with such mixtures are included in the scope of protection of this application.
The resin compositions contain an unsaturated prepolymer, that is, an unsaturated polyester or a vinyl ester or a vinyl ester urethane or mixtures thereof. The prepolymers usually have an average molar weight of at least 250 to at most 5000. Preferably, the average molar weight is in the range of 500 to 3500.
As the unsaturated polyester in the curable resin compositions according to the invention, use can be made of unsaturated polyesters with an acid number of less than 10 mg of KOH per g. Such unsaturated polyesters and their preparation are commonly known. They can be prepared from unsaturated polyesters having a higher acid number through e.g. a reaction with alcohols, glycols, ethylene carbonate, propylene carbonate, epoxy compounds, isocyanates or amines. See e.g. EP-A-0254186. It is also possible to use e.g. dicyclopentadiene-modified unsaturated polyesters. See e.g. G. Pritchard (Ed.), Developments in Reinforced Plastics—1 (1980), Applied Science Publishers Ltd, London, ISBN 0-85334-919-3, pp. 64-67. Preferably, the acid number is from 0 to 5 mg of KOH per g, most preferably in the range of from 0 to 3 mg of KOH per g.
All the known vinyl esters can be used as the vinyl esters (also referred to as epoxy (meth)acrylates in the literature) in the curable resin compositions according to the invention. Ethoxylated bisphenol-A-di(meth)acrylates and (unsaturated) polyesters with terminal (meth)acrylate groups are also classed as vinyl esters. The vinyl esters usually already have an acid number of less than 10 mg of KOH per g. Such vinyl esters and their preparation are commonly known. See e.g. G. Pritchard (mentioned above), pp. 29-58.
All the known vinyl ester urethanes can be used as the vinyl ester urethanes (also referred to as urethane (meth)acrylates in the literature) in the curable resin compositions according to the invention. The vinyl ester urethanes usually also have an acid number of less than 10 mg of KOH per g. Such vinyl ester urethanes and their preparation are commonly known. See e.g. U.S. Pat. No. 3,876,726.
Vinyl ester resins (epoxy (meth)acrylates) and vinyl ester urethane resins (urethane (meth)-acrylates) are usually very suitable for chemically stable applications.
The vinyl ether monomers that are used in the resin compositions according to the invention are vinyl ethers (or mixtures thereof) having the general structure according to formula (I) or (II):
A—CH═CH—O—R (I)
(A—CH═CH—O)
n
—R′ (II)
where A, R, R′ and n have the meanings indicated above.
Such vinyl ethers are commercially available. Examples of vinyl ethers that are suitable for use in the resin compositions according to the invention are the following compounds according to formula (I):
3-aminopropyl vinyl ether, t-amyl vinyl ether, butyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, 3-diethylaminopropyl vinyl ether, diethylene glycol monovinyl et
Udding Jan H.
Wolters Agnes E.
Asinovsky Olga
DSM IP Assets B.V.
Mayer Brown Rowe & Maw LLP
Seidleck James J.
LandOfFree
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