Stock material or miscellaneous articles – Composite – Of polyamidoester
Reexamination Certificate
2000-05-19
2002-09-24
Copenheaver, Blaine (Department: 1773)
Stock material or miscellaneous articles
Composite
Of polyamidoester
C428S423100, C428S423700, C428S424200, C428S492000, C428S500000
Reexamination Certificate
active
06455165
ABSTRACT:
BACKGROUND OF INVENTION
This invention relates to laminates having one layer of an olefinic unsaturation containing polymer and a second layer containing an active hydrogen containing polymer. The invention also relates to processes for the preparation of such laminates.
Due to the different chemical nature of polymers having olefinic unsaturation, such as rubber, and polymers having active hydrogen atoms, such as polyurethanes, it is difficult to form laminates from such polymers. One difference is the difference in surface energy of the polymers with the olefinic unsaturation containing polymers having a low surface energy and the active hydrogen containing polymers having a high surface energy. For instance, it is desirable to improve the performance of rubber based structures, such as tires, by bonding an elastomeric layer such as a polyurethane layer to the rubber layer. Unfortunately there are no elegant means for doing this.
What is needed is an adhesive which can bond a layer of an olefin containing polymer, such as rubber, to a layer of an active hydrogen containing polymer, such as a polyurethane. What is also needed is a process for bonding such layers together. What is needed is a laminate having a layer of an olefin containing polymer, such as rubber, and a layer of an active hydrogen containing polymer, such as a polyurethane.
SUMMARY OF INVENTION
The invention is a laminate structure comprising two or more layers of one or both of
a) a polymeric layer containing olefinic unsaturation; and
b) a polymeric layer having active hydrogen atoms; wherein,
c) an adhesive layer is located between the layers derived from one or more compounds having one or more nitrile oxide moieties;
wherein a portion of the nitrile oxide moieties, or derivatives thereof, is reacted with olefinic unsaturation of layer a), the active hydrogen atoms of layer b) or both.
In another embodiment the invention is a process for the preparation of such a laminate which comprises
i. contacting one or more layers of one or both of a) a polymeric layer containing olefinic unsaturation; and b) a polymeric layer having active hydrogen atoms; wherein c) an adhesive layer derived from one or more compounds having nitrile oxide moieties is located between the two layers; and
ii. heating the contacted layers to a temperature and under conditions such that the nitrile oxide moieties, or derivatives thereof react with one or both of the olefinic unsaturation of layer a) and the active hydrogen containing layer b).
The process of the invention allows relatively easy preparation of the laminates of the invention. The laminates exhibit properties attributable to the layers present. Such laminates are useful as tires, belts and hoses, for example.
DETAILED DESCRIPTION OF THE INVENTION
One or more layers of the laminate of the invention can be a polymer layer containing olefinic unsaturation.
Any polymer having olefinic unsaturation which is capable of reacting with a nitrile oxide moiety can be used in this invention. Preferable polymers containing olefinic unsaturation include rubber compositions, styrene-butyl rubber compositions, neoprene, ethylene-propylene terpolymers (prepared from ethylene-propylene-diene monomers, EPDM), monovinylidene aromatic monomer-conjugated diene block copolymers (such as block copolymers of styrene with butadiene or isoprene), polybutadiene, polyisoprene polychloroprene and the like. More preferred polymers containing olefinic unsaturation include rubber compositions, styrene-butyl rubber compositions, neoprene, ethylene-propylene terpolymers, monovinylidene aromatic monomer-conjugated diene block copolymers. Most preferred are natural rubber compositions and styrene-butyl rubber compositions. In one embodiment this polymeric layer may comprise a blend of polymers which contains at least one polymer with olefinic unsaturation. Preferably the polymer containing olefinic unsaturation has the olefinic unsaturation at the terminus of the polymer chain, i.e. has terminal olefinic unsaturation.
The other polymer layer may comprise a polymer having active hydrogen atoms which are reactive with nitrile oxide moieties or derivatives of such moieties. An example of such a derivative is an isocyanate moiety formed by the rearrangement of a nitrile oxide. For the purposes of this invention, an active hydrogen moiety refers to a moiety containing a hydrogen atom which, because of its position in the molecule, displays significant activity according to the Zerewitnoff test described by Wohler in the Journal of the American Chemical Society, Vol. 49, p. 3181 (1927). Illustrative of such active hydrogen moieties are —COOH, —OH, —NH
2
, —NH—, —CONH
2
, —SH, —COCH
2
CO—, —NHCONH—, —OCONH and —CONH—. Typical active hydrogen containing polymeric layers include polyurethanes having residual active hydrogen containing moieties, polyols, polyamines, polymercaptans polyacids, polymers derived from acrylics and methacrylics, and styrene-acrylate based random copolymers. Suitable Imino-functional compounds are those which have at least one terminal imino group per molecule, such as are described, for example, in U.S. Pat. No. 4,910,279, which is hereby incorporated by reference in its entirety. Preferably, the active hydrogen containing polymer has hydroxyl, amino, mercapto, carboxylic acid, urethane, urea, carbamate moieties, or a mixture thereof and more preferably amino moieties, hydroxy moieties or a mixture thereof. Preferably, the active hydrogen containing polymer is a polyurethane having residual active hydrogen containing moieties or a polyol such as a polyether or polyester polyol. The polymer containing active hydrogen containing moieties may be blended with other polymers or additives. Preferably such polymers are found in a solid form and are elastomeric or plastic in nature.
Suitable polyols useful include, for example, polyether polyols, polyester polyols, poly(alkylene carbonate)polyols, hydroxyl-containing polythioethers, polymer polyols, and mixtures thereof. Polyether polyols are well-known in the art and include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols which are prepared by reacting an unsubstituted or halogen- or aromatic-substituted alkylene oxide with an initiator compound containing two or more active hydrogen groups such as water, ammonia, a polyalcohol, or an amine. Such methods are described, for example, in U.S. Pat. Nos. 4,269,945; 4,218,543; and 4,374,210; which are hereby incorporated by reference in their entirety. In general, polyether polyols may be prepared by polymerizing alkylene oxides in the presence of an active hydrogen-containing initiator compound.
Preferable alkylene oxides include ethylene oxide, propylene oxide, butylene oxides, styrene oxide, epichlorohydrin, epibromohydrin, and mixtures thereof. Preferable initiator compounds include water, ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylol propane, pentaerythritol, hexanetriol, sorbitol, sucrose, hydroquinone, resorcinol, catechol, bisphenols, novolac resins, phosphoric acid, aliphatic and aromatic amines, and mixtures thereof.
Polyester polyols are also well-known in the art and may be prepared by reacting a polycarboxylic acid, or an ester or anhydride thereof with a polyhydric alcohol. Examples of preferable polycarboxylic acids include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, maleic acid, trimellitic acid, fumaric acid and terephthalic acid. Examples of preferable anhydrides include phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, maleic acid anhydride and glutaric acid anhydride., Mixtures of the polycarboxylic acids, esters and/or anhydrides described herein may be used. Examples of preferable polyhydric alcohols include ethylene glycols, propane diols, butane diols, 1,6-hexanediol, 1,8-octanediol, neopentylglycol
Bhattacharjee Debkumar
Knaub Philippe M.
Lysenko Zenon Z.
Schiff David E.
Copenheaver Blaine
Paulraj Christopher
Sims Norman L
The Dow Chemical Company
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