摘要:
Anionic polymerization initiators useful in the preparation of polymers having a protected amine functional group. The amine functionality includes a first protecting group, which can be aralkyl, methyl, allyl or tertiary alkyl group. The other of the amine protecting groups can be the same as the first protecting group. Alternatively, the second protecting group can be different from the first protecting group, in which case it is selected to have differential stability to agents used to remove the aralkyl, methyl, allyl or tertiary alkyl protecting group.
摘要:
Hetero-telechelic polymers having the formula: FGnull(Q)dnullZnullJnullnullA(R1R2R3)nullx nullnull(I) wherein FG is a protected or non-protected functional group; Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; d is an integer from 10 to 200; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; J is oxygen, sulfur, or nitrogen; nullA(R1R2R3)nullx is a protecting group, wherein A is an element selected from Group IVa of the Periodic Table of Elements; R1, R2, and R3 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, with the proviso J and FG are not the same, and processes for making the same.
摘要:
Hetero-telechelic polymers having the formula:FGnull(Q)dnullZnullJnullnullA(R1R2R3)nullxnullnull(1)wherein FG is a protected or non-protected functional group; Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; d is an integer from 10 to 200; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; J is oxygen, sulfur, or nitrogen; nullA(R1R2R3)nullx is a protecting group, wherein A is an element selected from Group IVa of the Periodic Table of Elements; R1, R2, and R3 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, with the proviso J and FG are not the same, and processes for making the same.
摘要:
The present invention is an improvement upon the known method of anionically polymerizing monomers by contacting the monomers with an anionic polymerization initiator which is an organo-substituted alkali metal compound. The improvement comprises decreasing the viscosity of the polymer cement by adding at least 0.01 equivalent of a metal alkyl compound per equivalent of alkali metal initiator if the metal alkyl is added before or at the beginning of polymerization. If the metal alkyl is added during the polymerization or after but before the living polymer is terminated, then at least 0.01 equivalent of the metal alkyl compound per equivalent of living polymer chain ends is should be used. The alkyl groups of the metal alkyl are chosen such that they do not exchange with the organo substituents of the alkali metal, which can be the living polymer chain ends or the organo substituents of the initiator. To avoid this undesired exchange reaction, the alkyl groups of the metal alkyl compound are selected to be more basic and/or less bulky or both than the organo substituents of the alkali metal compound.
摘要:
The present invention is an improvement upon the known method of anionically polymerizing monomers by contacting the monomers with an anionic polymerization initiator which is an organo-substituted alkali metal compound. The improvement comprises decreasing the viscosity of the polymer cement by adding at least 0.01 equivalent of a metal alkyl compound per equivalent of alkali metal initiator if the metal alkyl is added before or at the beginning of polymerization. If the metal alkyl is added during the polymerization or after but before the living polymer is terminated, then at least 0.01 equivalent of the metal alkyl compound per equivalent of living polymer chain ends is should be used. The alkyl groups of the metal alkyl are chosen such that they do not exchange with the organo substituents of the alkali metal, which can be the living polymer chain ends or the organo substituents of the initiator. To avoid this undesired exchange reaction, the alkyl groups of the metal alkyl compound are selected to be more basic and/or less bulky or both than the organo substituents of the alkali metal compound.
摘要:
In a process for the homopolymerization of vinylaromatic monomers or the copolymerization of vinylaromatic monomers and dienes in the presence of at least one alkali metal compound and at least one compound of an element of group 3a of the Periodic Table of the elements, the compounds contain, based on the sum of molar equivalents of alkali metal and elements of group 3a, in each case a) from 0.1 to 3.9 molar equivalents of oxygen, sulfur, nitrogen or phosphorus and b) from 0.1 to 3.9 molar equivalents of an organyl ligand.
摘要:
The initiation system comprises (1) at least one silylated initiator and (2) at least one alkaline metal alcoholate as ligand. The silylated initiator may be monofunctional and selected in particular from among the compounds of Formula (I) or difunctional and selected in particular from among the compounds of Formula (II): wherein R1, R2, R3 each independently represent a C1-C8alkyl radical, linear or branched; R4 is a linear or branched C1-C8alkylene radical; M is an alkaline metal or alkaline earth metal (valence q of 1 or 2); R5 and R6 each independently represent an alkyl radical, linear or branched, at C1-C8; R7, R8 each independently represent a C1-C8alkylene radical, linear or branched; M′ is an alkaline metal. Application is to the preparation of (meth)acrylic (co)polymers.
摘要:
The present invention relates to an initiation system comprising at least one initiator, with the exception of amides of alkaline metals, and at least one alkaline metal alcoholate of the formula ROM, in which M is an alkaline metal and R represents a group Q—R1—(OR2—)m wherein Q is a heterocyclic compound with 5 or 6 chain links, substituted or not, having 1 or 2 oxygen atoms as heteroatoms, R1 and R2 represent an alkylene group, linear or branched at C1-C4, and m is equal to 0, 1, 2 or 3. The present invention also relates to the application of the initiation system to the preparation of (meth)acrylic (co)polymers and, possibly, ethylenically unsaturated monomers that can be copolymerized with (meth)acrylic monomers.
摘要:
The invention relates to a process for the anionic polymerization and copolymerization of vinyl, dienic and heterocyclic monomers.According to the invention, the process consists in carrying out the reaction in the presence of an initiator consisting of a molecular combination of an alkali metal amide and the salt of the same alkali metal with at least one hydroxylic compound and in the absence of solvent. The initiator can be prepared by intimately mixing its constituents or in the presence of a solvent of low polarity which is subsequently evaporated off, or in situ in the monomer.Application to the synthesis of special or widely used polymers and copolymers.
摘要:
The invention pertains to a method for preparation of polymers, grafted polymers, and copolymers from olefins substituted by polar groups (ester, nitrile, or aryl) or from dienes, wherein the polymerization is initiated by the system formed by mixing of an organic amide of alkaline metal with an alkaline metal alkoxide. The organic amide is derived from primary or secondary amines or polyamines, or from tertiary polyamines containing at least one primary or secondary amino group. These amines contain N-C or N-Si bonds, 1-4000 C atoms and 1-1000 N atoms in a molecula, or have the molecular weight below 100,000. The alkoxides are derived from C.sub.3 -C.sub.16 alcohols. The polymerizations are carried out at -80.degree. to +80.degree. C. (advantageously at +20.degree. C.), at the monomer/organic amide molar ratio 5-1500, at the molar ratio alkoxide/amide 0.5-10, and in hydrocarbon or ether solvents. The advantage of organic amides of alkaline metals is the easy and economical preparation and suitable physical and chemical properties (solubility, higher resistance to contamination), while the alkoxide component exhibits the superadditive effect on the polymerization rate and yield and affects the microstructure of polymer. The method is also suitable for preparation of block copolymers by successive addition of various monomers, block copolymers with polyamine blocks, and grafted polyamine polymers.