KR850003546A - Preparation of "Active" Polymers - Google Patents

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Description

Preparation of "Active" Polymers

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Claims (32)

One or more monomers may be prepared under polymerization conditions with (i) an initiator of formula (R ¹ ) ₃ MZ and (ii) a source of fluoride, zanide, azide or non-fluoride ions, or an auxiliary cosolvent of suitable Lewis acid. By contacting to produce an "active" polymer having one or more monomer repeat units And his A polymerization method, which is further characterized by the following (a)-(h) in a method consisting of polymerizing monomers selected from the group consisting of mixtures. In the monomer structure, X is -CN, -CH = CHC (o) X 'or -C (O) X'; Y is -H, -CH ₃ , -CN or -CO ₂ R; Provided that when X is CH═CHC (O) X ′ Y is —H or —CH ₃ ; X 'is -OSi (R ¹ ) ₃ , -R, -OR or NR'R "; each R ¹ is independently a hydrocarbyl up to C ₂₀ ; R is one or more ether oxygen atoms in its aliphatic segment Is a hydrocarbyl up to C ₂₀ optionally containing one or more functional substituents which are non-reactive under polymerization conditions: R 'and R "are each independently selected from C _1-4 alkyl; In the initiator structure, R ¹ is as described above, Z is an activation substitution selected from the group consisting of the following structures and mixtures thereof X 'is as defined above; R ² and R ³ are each independently selected from hydrocarbyl up to C ₂₀ and H, optionally containing one or more ether oxygen atoms in their aliphatic segments and optionally containing one or more substituents which are unreactive under polymerization conditions; Z 'is 0 or NR'; m is 2,3 or 4; n is 3,4 or 5; M is Si, Sn or Ge Z just If M is Sn or Ge a) R ¹ is hydrogen or at least one of the R ¹ groups is not hydrogen b) R is a polymeric radical containing at least 20 carbon atoms and optionally containing one or more ether oxygen atoms in its aliphatic segment and optionally containing one or more functional substituents which are unreactive under polymerization conditions. c) at least one of the R groups in the monomer contains one or more reactive substituents of the formula -Z '(O) CC (Y1) = CH2, wherein Y ¹ is H or CH ₃ and Z' is as described above ) d) The initiator is of the formula (R ¹ ) 2 M (Z ¹ ) ₂ or O [M (R ¹ ) ₂ Z ¹ ] ₂ wherein R 1 and M are as defined above and Z is the activation limit. Wherein X ', R ³ , R ³ are as defined above and / or e) at least one of the R, R ² and R ³ groups in the initiator contains at least one initiator with the formula -Z ² -M (R ¹ ) ₃ wherein M and R 'are as defined above and Z ² is Activated radicals selected from the group consisting of: Wherein R ² , R ³ , X ', Z', m and n are as described above except that Z ² is Where M is Sn or Ge and / or f) Z is selected from the group consisting of -SR, OP (NR'R ") ₂ , -OP (OR ¹ ) ₂ , -OP [OSi (R ¹ ) ₃ ] ₂ and mixtures thereof, wherein R, R ¹ , R 'and R "are as described above and / or g) R ² and R ³ together represent a group of the structure Where Z is or And / or Z is And / or h) X 'and either R ² or R ³ are taken together Where Z is or And / or Z ² to be. The process of claim 1 wherein the process is performed at about −100 ° C. −150 ° C. 7. Polymers further characterized by the following (a)-(c) in an "active" polymer of the structure Wherein Z ″ is selected from the group consisting of And a and b are each independently selected from 0 or 1-100000 but (a + b) is at least 3 and Q is a divalent radical selected from the group consisting of X is -CH, -CH = CHC (O) X 'or -C (O) X'; Y is —H, —CH ₃ , —CN or —CO ₂ R provided that when Y is —CH═CH C (O) X ′, Y is —H or —CH ₃ ; X 'is -OSi (R ¹ ) ₃ , -R, -OR or NR'R "; each R ¹ is independently a hydrocarbyl up to C ₂₀ ; R is a hydrocarbyl up to C ₂₀ and optionally the aliphatic segment Contains one or more ether oxygen atoms and optionally one or more functional substituents which are non-reactive under polymerization conditions, R 'and R "are each independently selected from C _1-4 alkyl and R ² and R ³ are each Independently from H and C ₂₀ up to hydrocarbyl, optionally containing one or more ether oxygen atoms in its aliphatic segment; Z 'is 0 or NR', where R 'is as defined above, m is 2,3 or 4, n is 3,4 or 5 and M is Si, Sn or Ge. (a) R ¹ is H or at least one of the R ¹ groups is not H and / or (b) Z "is selected from -P (O) (NR'R ') ₂ , -P (O) (OR ¹ ) ₂ , -P (O) [OSi (R ¹ ) ₃ ] ₂ and -SR; / Or (c) the "active" polymer is of the formula Wherein R _p is an aliphatic, alicyclic, aromatic or aliphatic hydrocarbyl radical containing up to C ₂₀ or a p-valent polymerization radical containing at least 20 carbon atoms, optionally one or more ether oxygen atoms, keto groups and / or Or a functional substituted component which is non-functional in the polymerization condition; Z ³ is selected from the group consisting of: Z ', R ² , R ³ , X' m and n are as defined above and P is a divalent polymer radical of the structure Wherein X, Y, R, a and b are as defined above, Q, M and R ¹ are as defined above, k is 0 or 1 and p is an integer where at least 1 or k is 0 is at least 2 except (i) Z ³ Where M is Sn or Ge (ii) Z ³ is -Z'-C (O) If R ² and R ³ together And (iii) Z ³ R ² and X 'together to be. The polymer solution of claim 3 dispersed or dissolved in an aprotic solvent Film made from the solution of claim 4 Fiber made from the solution of claim 4 A coated substrate prepared from the solution of claim 4 The polymer capped with a capping agent according to claim 3 wherein the "active" ends contain at least one functional substitution which is non-reactive under capping conditions. A process for preparing a block copolymer from the "active" polymer of claim 3. A polymer produced by the method of claim 9. Castings made from the polymer of claim 3 A photosensitive product prepared from the polymer of claim 3. A process consisting of cooling an "active" polymer selected from the following structural formulas with an active hydrogen source. In the above formulas, Z "is selected from the group consisting of -P (O) (NR'R ") ₂ , -P (O) (OR ¹ ) ₂ , -P (O) [OSi (R ¹ ) ₃ ] ₂ and -SR; a and b are each independently 0 Or 1-100,000 but in which (a + b) is at least 3 Q is a divalent radical selected from the group consisting of: X is —CN, —CH═CHC (O) X ′ or —C (O) X ′; Y is -H, -CH ₃ , -CN or -CO ₂ R with the proviso that Y is -H or -CH ₃ when X is -CH = CHC (O) X ', X 'is _{^{-OSi (R 1) 3, -R}} , -OR , or NR'R ", and, R ¹ are each independently a hydrocarbyl of up to C ₂₀ R is optionally the aliphatic segment in a high to C ₂₀ hydrocarbyl in containing one or more ether oxygen atoms, and containing one or more non-reactive functional substituted minutes under the polymerization conditions, and optionally R 'and R "are each independently selected from C ₁ -C ₄ alkyl, R ² and R ³ are each Independently selected from H and C ₂₀ hydrocarbyl, optionally containing one or more ether oxygen atoms in its aliphatic segment and optionally containing one or more functional substituents which are non-reactive under polymerization conditions Z 'is 0 or NR' where R 'is as defined above, m is 2,3 or 4, n is 3,4 or 5, M is Si, Sn or Ge and R _p is C ₂₀ An aliphatic, alicyclic, aromatic or aliphatic hydrocarbyradic radical containing up to p-valent polymeric radicals containing at least 20 carbon atoms, optionally non-reactive under one or more ether oxygen atoms, keto groups and / or polymerization conditions Z ³ is selected from the group consisting of the following and mixtures thereof Is a divalent polymerization radical of the formula k is 0 or 1, p is an integer that is at least 1 when k is 1 or at least 2 when k is 0 (i) Z ³ Where M is Sn or Ge (ii) Z ³ If R ² and R ³ together And (iii) Z ³ If R ² and X 'together And (iv) one or two of the R ¹ groups are H when A ″ is any of the first 5 groups mentioned above. The product of the method of claim 13. A coating composition consisting of the product of the method of claim 13. An enamel coating composition comprising the product of the process of claim 13 and a crosslinkable functional group. The enamel coating composition according to claim 16, wherein the crosslinking functional group is provided by the melamine resin. The coating composition of claim 15 wherein the lacquer can be cured by solvent evaporation. A substrate coated with the coating composition of claim 15. A coated substrate coated with a plurality of layers of the enamel coating casting of claim 16 wherein at least one composition contains a pigment and at least the composition of the outermost layer does not contain a pigment. A coating composition composed of the product of claim 14. An enamel coating composition comprising the product of claim 14 and a crosslinking functional group. 23. The enamel coating composition of claim 22, wherein the cross-linking functional group is provided by melamine resin. The coating composition of claim 21 wherein the lacquer can be cured by solvent evaporation. A substrate coated with the coating composition of claim 21. A coated substrate coated with a plurality of layers of the enamel coating composition of claim 22 wherein at least one composition contains a pigment and at least the composition of the outermost layer contains no pigment. The coating composition of claim 21 in the form of a powder. The coating composition of claim 21 dispersed and / or dissolved in an aqueous medium. The coating composition of claim 21 suspended and / or dissolved in an organic liquid medium. An electrocoating composition comprising the product of claim 14. A coating composition composed of the product of claim 14 which can be cured by a material in vapor form. 23. The enamel coating composition of claim 22, wherein the crosslinkable functional group is provided by an isocyanate resin. ※ Note: The disclosure is based on the initial application.