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
2000-12-08
2004-12-14
Mullis, Jeffrey (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...
C525S317000
Reexamination Certificate
active
06831133
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to the preparation of allylated poly(vinyl chloride) by utilizing an allyltrialkylsilane in the presence of Friedel-Crafts acids. The pendant allyl groups can be further reacted through various functionalization reactions to contain groups such as epoxy, hydroxyl, and silyl. A method for determination of the labile chlorine content of poly(vinyl chloride) is also disclosed.
A further embodiment of the present invention relates to poly(vinyl chloride) grafted with an unsaturated hydrocarbon such as a diene to form a plurality of pendant hydrocarbon oligomers on the poly(vinyl chloride) chain, each having an unsaturated end group. A method for producing the poly(vinyl chloride) grafted dienes and the addition of various functional end groups to the oligomers is also set forth. In yet a further embodiment of the present invention, the functionalized end groups such as pendant —OH groups of both the allylated and diene grafted poly(vinyl chloride) are further reacted with other monomers or polymer chains which thus results in a poly(vinyl chloride) chain having pendant polymers. These compositions are useful as compatibilizers for poly(vinyl chloride) and various other resins.
BACKGROUND OF THE INVENTION
During polymerization of vinyl chloride to poly(vinyl chloride) (PVC), in addition to regular —CH
2
CHCl— repeat units, a very small quantity of “active” or “labile” chlorines also arises. Although the concentration of these active chlorines is very modest, their presence decisively influences the ultimate thermal, oxidative, and chemical stability of this commercially important resin. The literature is replete with references addressing details of this problem such as set forth in
Thermal Degradation of Some Model Compounds for Poly
(
vinyl chloride
), Airinei, Buruiana, Robila, Vasile and Caraculacu, Polymer Bulletin 7, 465-471, (1982);
Formation of Anomalous Structures in PVC and Their Influence on the Thermal Stability:
1
Endgroup structures and Labile Chlorine Substituted by Phenol
, Hjertberg, Soervik,
J. Macromol. Sci
., Chem. 1982 A17(6), 983-1004; and
Formation of Anomalous Structures in PVC and Their Influence on the Thermal Stability:
2.
Branch Structures and Tertiary Chlorine
, Hjertberg and Sorvik,
Polymer
, Vol. 24, June, 1983, pp. 673-684.
It has been found that the active chlorines in poly(vinyl chloride), in conjunction with certain Friedel-Crafts coinitiators, are efficient initiators for the grafting of cationically active monomers (isobutylene, styrene) from poly(vinyl chloride), and that the thermal stability of the grafted poly(vinyl chloride) increases significantly over that of unmodified poly(vinyl chloride). See for example
Cationic Grafting: The Synthesis, Characterization and Physical Properties of Poly
(
Vinyl Chloride
-
g
-
Isobutylene
), Kennedy and Davidson,
J. Macromol. Sci. Chem
., A12(2), pp. 197-207 (1978);
Poly
(
vinyl chloride
-
g
-
Styrene
):
Synthesis, Characterization, and Physical Properties
, Kennedy and Nakao,
J. Macromol. Sci
.-Chem., A12(2), pp 197-207 (1978);
Thermal Stability of Graft Modifications of PVC and Related Materials
, Abbas,
Journal of Polymer Science
: Polymer Chemistry Edition, Vol. 13, 59-68 (1975);
New Telechelic Polymers and Sequential Copolymers by Polyfunctional Initiator
-
Transfer Agents
(
Inifers
).
XVII. Epoxy and Aldehyde Telechelic Polyisobutylenes
, Kennedy, Chang, and Francik,
Journal of Polymer Science
: Polymer Chemistry Edition, Vol. 20, 2809-2817 (1982); and
New Telechelic Polymers and Sequential Copolymers by Polyfunctional Initiator
-
Transfer Agents
(
Inifers
).
III. Synthesis and Characterization of a Poly
(&agr;-
Methylstyrene
-&bgr;-
Isobutylene
-&bgr;-&agr;-
Methylstyrene
), Kennedy and Smith,
Journal of Polymer Science
: Polymer Chemistry Edition, Vol. 18, 1539-1546 (1980).
The active chlorine content in poly(vinyl chloride) has been determined by several groups by using FTIR and UV spectroscopy, and selective reactions in conjunction with IR- or UV-active reagents. The values reported in the literature cover quite a broad range (i.e. anywhere from 0.04 to 2.3 mol %), and the discrepancy cannot be explained only by the differences between the samples used. This uncertainty prompted us to develop an analytical method for the determination of the minute concentrations of active chlorines in poly(vinyl chloride) starting material.
SUMMARY OF THE INVENTION
The preparation of the allylated poly(vinyl chloride) is described herein. The active chlorines in poly(vinyl chloride) can be replaced by pendant allyl groups (—CH
2
CH═CH
2
) by the use of allyltrialkylsilane in the presence of Friedel-Crafts acids. The thermal stability of allylated poly(vinyl chloride) is significantly superior to that of the starting material. NMR analytical results of the allylated poly(vinyl chloride) can be utilized to determine the active chlorine content in poly(vinyl chloride). The allyl groups of the allylated poly(vinyl chloride) can be used in various functionalization reactions such as epoxidation, hydroboration, oxidation, and hydrosilation to respectively yield epoxy, hydroxyl, and silyl functional groups.
The poly(vinyl chloride) can also be cationically reacted with an unsaturated hydrocarbon such as a diene to produce a plurality of grafted oligomers pendant from the poly(vinyl chloride) backbone containing a plurality of unsaturated end groups such as allylic groups. The allylic or unsaturated end groups of the oligomeric branch can also be reacted to form various functional groups such as hydroxyl, silyl, or epoxy end groups. The various pendant functional end groups such as hydroxyl can be further reacted through various reactions to contain other oligomers or polymers such as various polyethers, polyesters, polyurethanes, polyamides, or polycarbonates. The resulting product can be described as a poly(vinyl chloride) chain having pendant or grafted oligomers or polymers, which are useful as compatibilizers for mixtures of poly(vinyl chloride) and various polymers.
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Encyclopedia of PVC, vol. 1, 2ndEd., Marcel Dekker, Inc. New York, (1986); pp. 570-605.
Heat Degradation of PVC Stabilized by Treatment with Alkylaluminum Compounds, Gupta and Kennedy,Makromol.Sci.-Chem., A12(10), (1978) pp. 1407-1426.
The Discoloration of PVC-I, Correlation Between the Dehydrochlorination and Discoloration of PVC, Levai and Ocskay,European Polymer Journal, vol. 10, Pergamon Press (1974), pp. 1121-1125.
Living Carbocationic Polymerization. XXX. One-Pot Synthesis of Allyl-Terminated Linear and Tri-Arm Star Polyisobutylenes, and Epoxy- and Hydroxy-Telechelics Therefrom, Ivan and Kennedy,Journal of Polymer Science: Part A: Polymer Chemistry, vol. 28, (1990), pp. 89-104.
Determination of Tertiary Chlorine Structures in PVC, Buruiana, Alrinei, Robila and Caraculacu,Polymer Bulletin 3, (1980), pp. 267-271.
Graft Modification of PVC and Related Reactions, Thame and Lundberg,Journal of Polymer Science: Part A-1, vol. 10, (1972), pp. 2507-2525.
Determination of Unsaturated Structures in PVC by Means of Fourier Transform1H-NMR Spectroscopy, Caraculacu and Bezdadea,Journal of Polymer Science: Polymer Chemistry Edition,
Kennedy Joseph P.
Pi Zhengjie
Mullis Jeffrey
Roetzel & Andress
The University of Akron
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