Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/81—Preparation processes using solvents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/40—Regeneration or reactivation

Definitions

• Polycellulose also known as polylactide
• the £S has caused a wide range of people.
• the method of poly Ui is currently a large number of ⁇ :, a method in which lactide is used for ring-opening polymerization.
• the early genus catalyst is subjected to ring-opening polymerization of lactide to prepare polylactic acid, such as CN1814644, CN181 5 and US5235031, US5357034, US 045418, US 057537, US3736646 contendbut this
• the class method takes a long time, and the polyUi of ⁇ is from the residue of * ⁇ 3 ⁇ 4, so ⁇ is applied to the biomedical, electronic, etc., then Connor et al.
• N-Heterocyclic Carbene Cuihua Agent The raw intermediate is the corresponding N-heterocyclic carbene, which is 1W extremely nucleophilic ⁇ ! ⁇ , attacking lactide turn during catalytic open-loop polymerization, rough opening Ring, the presence of the agent; 3 ⁇ 4 find the poly but the N-heterocyclic card filament hair, it is often sensitive, It is directly used to catalyze the polymerization, and the jump is catalyzed by the «marriage N-heterocyclic carbene precursor or N-heterocyclic carbene.
• the N-heterocyclic carbene such as N-heterocyclic card H-CC1 3 , €eF 5 , HR, etc., as the lactide ring-opening polymerization compound.
• the poly( ⁇ ) By controlling the poly( ⁇ ) , eliminating small substances such as €C1 3 , H-Qft, HR, etc., freeing the N-heterocyclic carbene, catalytic polymerization ⁇ (GrcgoiyW Nyce et al. Chemistiy-AEuropean Journal 2004, 10 , 073 ⁇ 1079; SzilMCsilion et al. Journal of the American Chemical Society, 2005, 127, 9079-9084).
• the card is contaminated with carbene dioxol ⁇ ; with its N-heterocyclic K3 ⁇ 4 ⁇ different, ! ii j (off C (3 ⁇ 4) temperature is the same, can be used in the in-situ carbene step, design card biology Control the emperor is difficult to step, t control the air polymerization process
• N-heterocyclic carbene catalyzes the ring-opening polymerization of lactide
• carbene dioxane ⁇ heterocycle is different, 1 to 2 and lactide ring-opening polymerization A, the nature of the product needs to be combined with the process of ⁇ ⁇ 3 ⁇ 43 ⁇ 43 ⁇ 4 There are rows in the circumference, that is, not all carbene dioxins are suitable for the vinegar ring-opening polymerization.
• a method for ⁇ 1 carbene dioxin « ⁇ entanglement of polyfiber, wherein the carbene dioxin « ⁇ woman mouth type (I) is as follows:
• X 1 is selected from S or oxime
• X 2 is selected from C or N
• R 1 , R 2 may be selected from hydrogen, 1 to 10 carbon atoms, 1 to 10 sub-micro halogen atoms Or one or more substituted filaments, 3-6 ring, halogen atom, bond ⁇ , 3 ⁇ 4 ⁇ ⁇ of the same or different groups in the sum
• R 3 , R 4 may be selected from hydrogen, halogen Atom, a beta, a submicrohalogen atom, a mouthful!
• the specific structure of the carbene dioxide represented by the formula (I) can be represented by the formula ( ⁇ ), the formula (m), the formula (IV) or the formula (V):
• R ⁇ R 2 can be self-hydrogenated, 1 ⁇ 10 1 ⁇ 10 ⁇ sub-halogen, hydroxyl, and paste! One or more of the substituted, 3-6 ⁇ mw ⁇ , halogen atom, pray, the same or different fine in the mouth; R 3 , R 4 may be selected from hydrogen, halogen atom, recorded, The remainder of the beta,
• sub-halogen atoms one or more substituted filaments, 3 ⁇ 4 ⁇ taken from the same or different groups in ⁇ 3 ⁇ 4 ; ⁇ 11 3 and 11 4 form ⁇ 3 ⁇ 8 ⁇ sub-rings Women's base ⁇ 11 3 and 11 4 shape 3 ⁇ 4 ⁇ .
• R 1 R 2 may be selected from hydrogen, 1 to 10, 3 ⁇ 4&, 1 to 10, halogen atoms, hydroxyl groups, and a mouthful! One or more substituted in ⁇ , 3-6 ⁇ mw ⁇ , halogen atom, prayer silk, paste
• R 3 and R 4 may be selected from hydrogen, halogen atom, recorded, and the remainder of ⁇ .
• R 1 may be selected from hydrogen, 1 to 10, l ⁇ l.
• R 3 , R 4 may be derived from hydrogen, a halogen atom , the same or different groups in the 3 ⁇ 4 3 ⁇ 4 ⁇ group substituted by one or more of a halogen atom, a hydroxyl group, or a benzene;
• R 3 and R 4 form 3-8 ⁇ mf ⁇ ⁇ ⁇ R 3 and R 4 are not.
• R 1 R 2 may be selected from hydrogen, 1 to 10 1 to 10 atoms, hydroxyl groups, and a mouthful! One or more substituted in ⁇ , 3-6 ⁇ mw ⁇ , halogen atom, prayer silk, paste
• R 3 may be selected from the group consisting of hydrogen, a halogen atom, a single, a sub-microhalogen atom, a hydroxyl group, and one or more substituted in the benzene group.
• R 2 and R 3 are bonded to the i3 ⁇ 4 six-membered N-heterocyclic ring.
• _h3 ⁇ 4 ⁇ 3 ⁇ 4 can be monosubstituted, substituted, ⁇ can be the same or different, take ⁇ ⁇ from i ⁇ 5 broken atomic filaments, l ⁇ 5 sub-halogen atoms, recorded, living! One or more substituted filaments in ⁇ , halogen atom, hydroxyl group, ⁇
• _hj4 Polyfiber method can ⁇ ⁇ Poly &»t Bin dioxo «* ⁇ /, agent and lactide turn • t mrby 1: 0.2-5: 2 ⁇ 10000, ⁇ ⁇ 7 ⁇ : 0.5-3: 1 ( ⁇ 500, especially ⁇ ⁇ 71: 0.5-2: 100 ⁇ 3 ⁇ ⁇ ⁇ agent; 1 ⁇ 23 ⁇ 4t ⁇ -50 ⁇ 25(FC, ⁇ ⁇ J 50°C ⁇ 180°C, ⁇ ⁇ J 6(FC ⁇ 150 o C; ⁇ time is 3 seconds to 120 hours, ⁇ ⁇ 7 ⁇ ⁇ 2 ⁇ 24 hours, especially ⁇ ⁇ 7 ⁇ . 2 ⁇ 15 hours.
• the method of polyfibrin can also be used to collect &<tb> bis, oxime, and lactide massage ratio 1: 02-5: 2 ⁇ 10000,
• the ⁇ 3 ⁇ 41 ⁇ 2 agent may be ⁇ Bf ⁇ ethanol, n-propanol, isopropyl ⁇ n-butanol, tert-butylphthalide, ⁇ ⁇ .
• weak acid such as tannic acid, acetic acid, thin ship, etc.
• the hydrazine solvent used may be cyclohexane, 3 ⁇ 4 ⁇ 4, diethyl ether, acetone, cyclohexanone, dioxane, tetrahydrofuran, south, clumsy, diphenylbenzene, dichlorodecane, ⁇ ! Alkane, -dimercaptopurine, climbing bismuth base ⁇ «fc ⁇ ⁇ ⁇ acetone, tetrahydrofuran p, benzene, diphenyl, chlorin, ⁇ !
• the amount of ⁇ ⁇ lactide can be 0.01molL ⁇ 10molL, ⁇ 70.5molL ⁇ 5molL, especially ⁇ 70.5molL ⁇ ; 3molL.
• ⁇ can be carried out in a ball inert gas, the inert gas argon nitrogen Purified in ethanol or water.
• the forest body is gathered, ⁇ ball is inert! ⁇
• the gas is hollowed out, the inertia is mentioned.
• the gas is 3 ⁇ 4 ⁇ 7 ⁇ .
• the nitrogen pressure is 4 ⁇ 20 milli ⁇ .
• the solvent is curbed, for example Purified by decyl alcohol, ethanol or water, the agents are dichlorodecane, ⁇ ! alkane, toluene, benzene, propane ⁇ tetrahydrofuran, H decane, decane, tetrahydrofuran p .
• carbene dioxin ⁇ * ⁇ is a catalyst, which contains different s? ⁇ ; carbene dioxins, and different «it rates under 3 ⁇ 41, because ofc can be sieved
• Carbene dioxin « ⁇ is a ring-opening poly-fiber-conducting agent, and the ring-opening polymerization of lactide is carried out in an empty system; after COzto escapes, it does not bring contaminants into the polymerization system.
• Figure 2 1 H NMR spectrum of poly Ui found with 1,3-3 ⁇ 4(2,6> acetonitrile p-2 ⁇ 3 ⁇ 4 ⁇ as catalyst;
• Figure 3 ⁇ - ⁇ , ⁇ -2 Cuihua agent ⁇ ] ⁇ found the poly Ui resistance color i in the analysis of the i-drying ° °
• ⁇ it ⁇ is 1 H NMR 3 ⁇ 4 ', 3 ⁇ 4 ' ⁇ H3 ⁇ 4 bribe cattle: nuclear magnetic ⁇ # ⁇ (BnjkerDRX500), with J-HCls ⁇ DMSO or d" H 3 COCH 3 as a solvent.
• Example 2 Place 13- ⁇ (o- ⁇ 13 ⁇ 4) in a sitting *2"3 ⁇ 4 ⁇ (J) (73.54mg, 250 ⁇ phenylhydrin (5.4mg, 50 ⁇ L lactide (0.72g, 12.5mmol)
• 3 ⁇ 4 ⁇ 3 ⁇ 4 is 34,900, and ⁇ lPDI is 128.
• the amount is 26320 and ⁇ lPDI is 1.06.
• 3 ⁇ 4 ⁇ 3 ⁇ 4 is 18,850, and ⁇ lPDI is 1.08.
• 3 ⁇ 4 ⁇ 3 ⁇ 4 is 18,800, and ⁇ lPDI is 128.

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