TW200817445A - Hyperbranched polymers or compounds and methods of making same - Google Patents

Abstract

Hyperbranched polymers or compounds are prepared by a simple polymerization of monomers or compounds A2 with difunctional groups of type A, and Bf having f-functional groups B, and AR or A'R with mono-functional group A or A', wherein f equals 3 or is larger than 3. The groups A, A', and B can not react with themselves, but group B can react with A or A'.

Description

200817445 IX. Description of the invention: [Technical field to which the invention belongs] Product preparation method for the preparation of a polymer compound having a multi-branched structure and a dragon agent, a rheology modifier, a drug delivery material, a nonlinear optical material , chelation = use of nanoparticles and other uses.力月匕1±微/ 【Prior Art】

Different from traditional linear, branched and reticular structure classification of polymers, in recent years, many new polymers have been developed and synthesized, such as star-shaped, ladder-like, comb-like, dendritic 'super-branched ^ polymers, all of which are subject to Great attention is paid to the dendrimer as an example. Due to its special structure, it has low viscosity, high solubility and high functional density. It is expected to be used as a toughening agent, a drug delivery material, and a non-material. Linear optical materials and nano self-assembled structures. However, the = tree dendrimer synthesis step is complicated, and it is difficult to use one-pot preparation, so that it cannot be produced in large quantities. "In contrast, another polymer with a multi-branched structure: hyperbranehed polymer, although its structure is not as simple as a dendrimer, and still has the special properties of many dendrimers, super Branched polymers are easily synthesized using AB, a type of monomer including a monofunctional group a, and two or more functional groups B, wherein the functional sigma groups A and B can form a bond and function The bases A and A do not form a bond, and the functional groups B and B do not form a bond. A one-pot step-wise polymerization is carried out to prepare a ruthenium molecule which produces a super-branched structure, American Chemical Society, Polymer Preprints, Division of Polymer Chemistry 29, 1988 (310-311) discloses the use of AB, a monomer to synthesize polyphenylene super-branched polymers, which has attracted extensive attention. U.S. Patent 5,514,764 discloses the use of the AB2 type monomer synthesis. Super-branched structure polyesters and polyamines, U.S. Patent 6,525,170 discloses the use of an epoxy group-containing oxime-containing ABf-type monomer to synthesize a super-branched polyester. U.S. Patent No. 6,979,737 discloses the use of the AB2 type. Monomer synthesis of super-branched polyether ketone. Although the AB/type monomer method can easily prepare a variety of super-branched polymers, it is limited by the fact that most AB/monomers have not yet been mass-produced. The laboratory is small-scale synthesis, difficult to generalize, and mass-produced. In addition, Macromolecules, 32, 1999 (p. 6380-6382) reveals that the A2 and B3 bi-monomers are dissolved in a large amount of solvent to prepare a super-branched polyether. The 10% strategy still faces many challenges. 200817445 A large amount of solvent must be used, and the reaction time is, for example, to avoid gelation to form a network structure, which is too long, and the manufacturing cost is increased, and it is still difficult to mass-produce.

': Wide-species containing * functional group A, the compound (10) m) produces a branched high: S °, a medium functional group VIII can form a bond, JL functional group A, and B can form and a functional group A A does not form a bond, and the functional group A, and A, do not form a bond, and the functional group A and A are not bonded, and the branched polymer or compound produced by the present invention can be used as an increase. Paste, rheology change _, drug delivery materials, nonlinear optics (4), chelating agents, j-like micro-negative green, etc. Wherein, the addition of a suitable amount of the monofunctional group-containing filament A, the compound in the poly a reaction, competes with the (iv) energy-based compound, and competes with the functional group, thereby forming a chain at the end of the molecule to avoid formation of a three-dimensional network structure. By gelation, it is possible to produce a super-branched knife or a compound. The advantage of the present invention is a one-pot polymerization reaction in which a reaction is carried out in a small amount of solvent or solvent-free conditions, thereby shortening the reaction time and mass production.

Another feature of the present invention is that the present invention can utilize most of the commercially available difunctional A-containing monomers or compounds (VIII), and at least one monomer having 3 or more functional groups B or The compound (Bf), and at least one monofunctional group A or A, and the compound (AR or A, R) produce a branched polymer or a compound in which the functional groups VIII and 3 can form a bond and function. The base A, and B can form a bond, and the functional group A and A do not form a bond, and the functional group A, and A, do not form a bond, and the functional groups a and a do not form a bond, and further, when reacted A specific functional group is formed, and an advantage of the present invention is that a branched polymer or compound having a specific functional group can be produced by this method, for example, A is an epoxy group, B is an amine group, and an epoxy group is formed after ring opening. A hydroxyl group can be used to produce a polyhydroxy branched polymer or compound by this method. Another feature of the invention is that the invention can utilize most of the commercially available difunctional A containing monomers or compounds (VIII), and at least one monomer or compound containing 3 or more functional groups B. (Bf), and at least one compound containing a monofunctional group of eight or eight (AR or A, R) to produce a branched polymer or compound, wherein the functional groups A and B can form a bond, and the functional group A, B can form a bond, and the functional group A and A do not form a bond, and the functional group A, and A, do not form a bond, and the functional groups A and A, do not form a bond, wherein the double functional group A The compound or compound (A), or the monomer or compound (Bf) containing polyfunctional B, or the compound (AR or A, R) containing monofunctional A (or A) additionally has a functional group D' The functional group D does not participate in the reaction or the reactivity is small, and the advantage of the present invention is that it can be used as the side of 200817445 or 4_chlorobenzenethiol, l,3-dimercaptopropane, 1-naphthalenemethanethiol. The materials listed above and the following examples are intended to clearly illustrate the advantages of the characteristic fish of the present invention and are not intended to limit the scope of the invention. Example 1 : Adipic acid (A2), with glycerol (giycero b b3), and n-hexanoic acid (n-Hexan〇ic)

Acid acid 'AR) 'and dibutyloxy>[匕锡' is added to the reaction tank in different proportions and heated, wherein the acid and alcohol are subjected to the overall polymerization and esterification reaction (150〇c, 2 hours) to produce more soluble The molecular weight of the product can be adjusted according to the composition of the raw materials. The results are shown in Table 1, wherein the molecular weight is determined by a gel permeation chromatography (GPC), and the standard is polystyrene (the same applies hereinafter). Table 1 : In Example 1, the weight and number average molecular weight of the different raw material composition products (=^, the molar ratio of the raw material to adipic acid: glycerol: n-hexanoic acid 1.0: 2.0: 4.0 Mw 17693 Μη 3340 1.0:3.0: 7.0 3653 1225 Example 2: ethylene glycol diglycidy ether (Dow, DER 230) ' with polypropyl scale diamine (p〇iy〇Xypr〇pyiene diamine, jeffamine D230), with glycidol The phenyl glyddyl ether (PGE) is added to the reaction tank in different proportions and then heated to carry out the overall polymerization reaction. The epoxy group is opened to react with a hydroxyl group, and the product is soluble in tetrahydrofuran (THF). According to the composition of the raw materials, the results are shown in Table 2. Table 2 · The weight and number average molecular weight of the raw materials of different raw materials in Example 2. The molar ratio of raw materials to Mw Μ EGDE: D230: PGE 1.0: 1.0: 2.0 12333 3611 1.0 :2.0:6.0 5964 1 3181 200817445

«V Example 3: Bisphenol A epoxy resin (Dow, DER·332, EEW=173), added to the reaction tank in different proportions with sulfanilamide (SAA) and glycidyl anisole (pge) After mixing, heating is carried out to carry out an overall polymerization reaction, which causes a ring opening reaction to produce a hydroxyl group, and the molecular weight of the product can be adjusted according to the composition of the raw materials. The results are shown in Table 3. Table 3: In Example 3, the weight of the different raw material composition products and the number average molecular weight. Raw material molar ratio DER332:SAA:PGE Mw 24596 Μη 7724 1.0:1.0:2.0 1.0:2.0:6.0 13778 5310 Example 4: Double Α 衣 衣 氧基 曰 (Dow ' DER 332), with diethylene Diethylene triamine 'DETA' and phenyl glycidyl ether (PGE) were added to ethanol in different proportions (reactant 50% by weight), mixed and heated for 2 hours (60 ° C, reflux), wherein the ring After the oxy ring opening reaction, a hydroxyl group is produced, and the product is soluble in tetrahydro 11 pentane (Thf), and the molecular weight can be adjusted according to the composition of the raw materials. The results are shown in Table 4. Table 4 - In Example 4, the weight of the different raw material composition products and the number average molecular weight. Raw material molar ratio DER 332: DETA: PGE 1.0: 1.6: 6.0 Mw T7093 Μη ~ 4260 1.0: 1.8: 7.0 14488 3850 1.0: 2.0: 8.0 9425 3229 Example 5: Double-anti-A epoxy resin (D〇w, deR 331, EEW = 186), mixed with polyamine-based compound (ylene triamine ' DETA ' and phenyi giyeidyl ether ( ^GE ) ^ in a reaction tank and heated to carry out the overall polymerization , wherein the epoxy group is subjected to a ring opening reaction to produce a hydroxyl group, and the product is soluble in acetone or tetrahydrofuran (THF), and the molecular weight can be adjusted according to the composition of the raw materials. The results are shown in Table 5. 11 200817445 Table 5: In Example 5, the weight and number average molecular weight of different raw material constituents and their glass transition temperature 'where the glass transition temperature is measured by the differential thermal card (10) c), the rate of helium increase is 10oC/min. DER, 331; DETA: PGE Mw Μη Tg (°C) 1.0: 1.6: 6.0 26932 7485 33 1.0: 2.0: 8.0 3556 1527 26 Example 6: Bisphenol A epoxy resin (Dow, DER·332, EEW=173), and diethylenetriamine (DETA), and glycidyl anisole (phenylgtycidyletl^r, PGE) are added to the reaction tank in different proportions and heated, wherein the epoxy group is opened and reacted. Hydroxyl groups are produced, and the product is soluble in tetrahydrofuran (THF). The molecular weight can be determined according to the composition of the raw materials, and the results are shown in Table 6. Table 6: In Example 6, the weight and number average molecular weight of the different raw material composition products and their glass transition temperatures. W' Raw material molar ratio Mw Μη Tg (°C) DER 332: DETA: PGE 1.0: 1.8: 7.0 12564 3341 32 1.0: 2.0: 8.0 11007 3358 26 Example 7: Double-looking A epoxy resin (Dow, DER 332), with diethylene triamine 'DETA' and monoepoxy compound: glycidyl methacrylate (glycidyl methacrylate) (GMA) is added to the reaction tank in different proportions and heated, the product is The mercaptopropene-based multi-branched polymer can be dissolved in tetrahydrofuran (THF), and the molecular weight can be adjusted according to the composition of the raw materials. The results are shown in Table 7. 12 200817445 Table 7: In Example 7, the weight and number average molecular weight of the different raw material composition products. Raw material molar ratio D.E.R. 332: DETA: GMA Mw Μη 1.0:1.6:6.0 10250 2778 1.0:2.0:8.0 8947 2045 [Simple description of the diagram] None [Main component symbol description] None 13

Claims (1)

200817445 1 X. Patent application scope: '1· A synthetic method for producing a super-branched polymer or compound, which comprises using at least one monomer or compound containing a difunctional group A, and at least one containing 3 or 3 The monomer or compound of the above functional group b is reacted with at least one monomer or compound containing a monofunctional group A or A to produce a hyperbranched polymer or compound in which the functional groups A and B can form a bond. And the functional groups A' and B can form a bond, and the functional groups A and A do not form a bond, and the functional groups a, and a, do not form a bond, and the functional groups A and A do not form a bond. 2. The method as recited in claim 1, wherein the functional groups A and B, or the functional groups A, and B can form a bond and produce a specific functional group, thereby producing a super-branched shape having a specific functional group. South molecule or compound. f, 3. A method for synthesizing a branched polymer or compound, which comprises using at least one monomer or compound containing a difunctional group A and a functional group D, and at least one containing 3 or more B The monomer or compound of the energy group B is reacted with at least one monomer or compound containing a monofunctional group A or A to produce a hyperbranched polymer or compound in which the functional groups A and B can form a bond. And the functional group A, and B can form a bond, and the functional group A does not form a bond with the ruthenium, and the functional group Α' and Α' do not form a bond, and the functional group Α and Α do not form a bond, And after the reaction, the product retains all or part of the functional group D which fails to participate in the reaction, and a super-branched local molecule or compound having the functional group d is produced. 4. A method of synthesizing a branched polymer or compound, comprising using at least one monomer or compound containing a bis-energy group A, and at least one having three or more functional groups B and a fluorene-containing functional group A monomer or compound of D, which reacts with at least one monomer or compound containing a monofunctional group a or A, to produce a hyperbranched polymer or compound wherein the functional groups VIII and 8 can form a linkage 'and a functional group The bases A' and B may form a bond, and the functional groups eight and eight do not form a bond, and the functional groups A' and A' do not form a bond, and the functional groups are eight and eight, do not form a bond, and after the reaction The product retains all or part of the functional group D which does not participate in the reaction, and produces a hyperbranched polymer or compound having a functional group oxime. 5. A method for synthesizing a branched polymer or compound, which comprises using at least one monomer or compound containing a difunctional group A, and at least one monomer or compound having 3 or more functional groups B And reacting with at least one monomer or compound containing a monofunctional A or A' and a functional group D to produce a hyperbranched polymer or compound in which the functional groups VIII and 6 can form a bond, and the functional group A , and B can form a bond, and the functional groups eight and eight do not form a bond, and the functional groups A' and A' do not form a bond, and the functional groups A and A do not form a bond, and after the reaction A super-branched southern molecule or compound having a functional group D is produced by generating a functional group D in which all or part of the product is not involved in the reaction. 6. The method described in clause 1, 2, 3, 4 or 5 of the patent, wherein a monomer or compound containing a bifunctional group A and a monomer or compound having three or more functional groups B The molar ratio is from 1 to 0.1 to 1 to 20, and the molar ratio of the monomer or compound containing a difunctional octene to the monomer or compound containing a monofunctional a or A is from 1: to 1: 1 〇 Hey. 7. A method as described in claim 1, 2, 3, 4 or 5, wherein a monomer or compound containing a difunctional A group and a monomer or compound having three or more functional groups 8 The molar ratio of the molar ratio is from 1 to 1 to 1 to 10, and the molar ratio of the monomer or compound containing the difunctional A to the monomer or compound containing the monofunctional A or A, is 1:1 to 丨: 2〇. 〇8. The method as described in claim 2, 3, 4, 5, 6 or 7 wherein the functional group, the base A, the A'4B* are selected from the group consisting of an epoxy group, an amine group, and a carboxylic acid group. , anhydride, imidazolyl, hydroxy, phenolic, cyanate, nitrile, helium, alkenyl, boric acid, alkoxy (alk〇xyl), thiol, ethylene sulfhydryl, cyclic amine, nitro, jun A combination of a base, an ether group, an ester group, a base, a chloro group or a bromo group. • 9. The method as described in Sections 2, 3, 4, 5, 6, 7, or 8 of the patent application, which includes the use of the following combination of two or more polyfunctional compounds: a polycyclic ring An oxy compound, a polyamine-based compound, a polyvalent hydroxy compound, a polyvalent carboxylic acid-based compound, a polybasic acid anhydride-based compound, a polybasic cyanate-based compound, or a polyvalent fluorenyl-based compound, and includes a combination of the following compounds containing a single S: A monoepoxy compound, a monoamine compound, a monomolecular compound, a monoanhydride based compound, a monocarboxylic acid based compound, a monocyanic acid based compound, a monoalkenyl compound, or a monofluorinated chlorine based compound. '10. The method as recited in claim 2, 3, 4, 5, 6, 7, or 8 includes the use of the following combination of two or more polyfunctional compounds: a polyepoxy group A compound or a polyamine-based compound, and includes a combination of the following monofunctional group-containing monoepoxy compound 'monoamine-based compound, or a mono-alkenyl compound. 11. The method as recited in claim 2, 3, 4, 5, 6, 7, or 8, which comprises the use of the following combination of two or more polyfunctional compounds: a polyhydroxy compound or a poly A carboxylic acid-based compound, and includes a combination of the following monofunctional group-containing monohydroxy compound, monocarboxylic acid compound, or monoalkenyl compound. 12. A super-branched southern molecule or compound produced by the method described in claim 2, paragraphs 3'3, 4, 5'6, 7, 8, 9, 10 or 11. 15